TW200819417A - The method of manufacturing 2,2-bis(4-isocyanatophenyl)propane without phosgene and the intermediate products thereof - Google Patents

Abstract

The present invention provides the method of manufacturing 2,2-bis(4-isocyanatophenyl)propane without phosgene. The phenol released from bond breaking of bisphenol A (BPA) in acidic intermediate and produced from the alkyl group exchange process of aromatic urethane can be gradually removed out by the depressure method to accelerate the alkyl group exchange reaction and to obtain main product diamine formate finally. This diamine formate can further proceed high-temperature cracking reaction in the solvent with high boiling point to produce the 2,2-bis(4-isocyanatophenyl)propane used to manufacture aromatic polyurethanes, PU having anti-yellowing capability.

Description

200819417 IX. INSTRUCTIONS: [Invention Background] Aromatic isocyanates are chemical materials with great market demand and can be used as raw materials for polyurethane polymers, among which TDI and 4,4 / -MDI are the most bulk. Among them, because 4,4 'MDI has a higher boiling point and a lower toxicity phase, the PU product obtained has excellent performance and is preferred by the industry. Currently, the most effective method for producing aromatic or aliphatic isocyanates is the phosgene method, which is a well-known and well-developed technology. The isocyanate is formed by the action of a diamine and phosgene and the initial formation of Carbamic acid, followed by removal of hydrogen chloride. However, the phosgene is dangerous in operation. After the reaction, a large amount of hydrogen chloride is generated, which easily corrodes the reactor and other plant equipment, and is likely to cause environmental pollution. Therefore, the non-phosgene process of isocyanate needs to be developed. The PU polymer made of 4,4 'MDI has a fast reaction speed and excellent mechanical properties. However, after UV light or long-time oxidation, it usually has yellowing phenomenon. The reason is because the hydrogen on the Methylene structure connecting the two benzene rings is easily substituted after UV irradiation or oxidation to generate free radicals, thereby forming a structure of conjugated double bonds between the two benzene rings, resulting in serious The phenomenon of discoloration. 2,2-bis(4-isocyanatophenyl) propane (BCPP), an aromatic isocyanide chemically similar to 4,4 'MDI An acid salt compound whose structure is linked by an Isopropylidene structure to two isocyanate-containing benzene rings, different from the Methylene structure of 4,4 'MDI, which is attached to the methyl group of the ring due to its chlorine It is replaced by two methyl groups, so it is less susceptible to attack by oxygen or free radicals to form free radicals. Therefore, if BCPP is used to fabricate PU polymer, the structure of Isopropylidene is less likely to produce a structure with a double bond between two benzene rings under illumination and oxidation. Therefore, it is estimated that BCPP can be used to improve 200819417 4 , 4 'MDI PU polymer discoloration phenomenon. There are also reports and conclusions in the literature (τ· Servay et al., Polymer 41 (2000), 5247-5256).

Houser et al., in US Pat. 6 063 892, mentions the synthesis of 2,2-bis(4-isocyanatophenyl)propane, but its synthesis is a multi-step synthesis procedure, which is inconvenient and requires in the process. The use of phosgene is the main drawback of this method. The method described above is obtained by alkylating -methyl styrene with benzene, then obtaining 2,2-bis(4-aminophenyl) propane by nitration, hydrogenation, etc., and finally reacting with phosgene. In addition, Sundermann et al. also mentions in U.S. Pat. No. 4,388,246, the disclosure of the disclosure of the <RTIgt; The method of salt. Therefore, the present inventors adopted a safer and more environmentally friendly method of producing 2,2-bis(4-isocyanatophenyl)propane in a two-step process from BPA through a urethane precursor. SUMMARY OF THE INVENTION It is an object of the present invention to provide a bisphenol A (BPA, H-Bisphend A) having a difunctional group per organism which can be used for the production of 2,2-bis(4-isocyanatophenyl)propane. Another object of the present invention is to provide a non-phosgene process for producing 2,2-bis(4-isocyanatophenyl)propane, which has better safety and low pollution, and can be applied to the anti-yellowing fragrance. Group of polyurethane polymers. The bifunctional BPA derivative of the present invention has the following structural formula (ΠΙ);

ROOCHN

NHCOOR (III) wherein R is a C1 to C6 alkyl group, preferably a methyl group or an ethyl group. 200819417 The process for producing a β-pα derivative having a bifunctional group according to the present invention comprises the steps of: (a) subjecting a hydrazone of the formula (1) with a monofunctional aromatic urethane of the formula (II) in an acidic medium to remove hydrazine-alkane a trans-alkylation reaction to synthesize a compound of formula (III);

σ (II)

NHCOOR The above molar ratio of bisphenol A (ΒΡΑ) to monofunctional aromatic urethane is 1: 1~1: 10, preferably 1: 2~1: 5; biguanide and acidic medium The molar ratio is 1: 1 to 1: 20, preferably 1: 2 to 1: 7. The acidic medium is not strictly limited, and is preferably sulfuric acid (H2S, methanesulfonic acid (CHsSCbH) or p-toluenesulfonic acid. Preferred reaction conditions include: temperature 40~ 100 ° C, a pressure of 0.1 to 20 mmHg, a time of 0.5 to 2 hours. The 2,2-bis(4-isocyanatophenyl)propane produced by the non-phosgene method of the present invention has the following structural formula (IV) :

OCN

NCO (IV) The process comprises the steps of: (b) subjecting the BPA derivative of the above formula (III) to a high temperature thermal cracking reaction in a high boiling solvent. The high boiling point solvent of the above step (b) means that its boiling point is higher than 22 (TC; for example, but not limited to, diphenyl ether, phenyl cyclohexane. Derivatization of formula (III) The concentration of the solution formed by the substance and the high boiling point solvent is preferably 3 to 5 wt%. The preferred reaction conditions of the step (b) include: the temperature is 220 to 27 (TC, the time is 1 to 4 hours. 200819417 2 of the present invention , 2-bis(4-isocyanatophenyl)propane is mainly used in the manufacture of anti-yellowing aromatic polyurethane polymers (PU). [Methods of Implementation] A preferred embodiment of the present invention is methyl N -Methyl phenyl carbamate (MPC) or ethyl N-phenyl carbamate (EPC) as the reactant 'and proceed with the low-cost dihydric phenol BPA under acidic conditions' The dibasic carbamate can be directly prepared by removing the phenol and the alkane exchange reaction. There are various methods for synthesizing the carbamate compound in the literature, for example, Zajacek nitrobenzene in US Pat. 3 895 054, Methanol (or ethanol) and carbon monoxide are catalyzed by metal selenium (Selenium, Se) to produce MPC ( Or EPC), Fukuoka produces EPC from phenol, ethanol, carbon monoxide and oxygen in palladium (Palladium, Pd) at US Pat. 4 621 149. Our experimental preparation steps for the sake of simplicity, with phenyl isocyanate ( Phenyl isocyanate) is the starting agent as follows: Take a 250 ml 3-neck round bottom flask, place the magnet and phenyl isocyanate (71.4 g, 0.6 m), and separate the thermometer and isostatic The liquid funnel was placed on the apparatus. Methanol (48.0 g, 1.5 m) was placed in an isocratic separatory funnel, and slowly dropped into the reaction flask, and the flask was cooled in an ice bath. When the methanol was dropped ( Stirring for about 1 hour in 60 minutes), the infrared spectrum (IR) was sampled at intervals until the -NC0 absorption peak (2260 0^1) disappeared, and the reaction was stopped. The excess methanol was concentrated and concentrated under reduced pressure. The crude product was obtained as a white solid, which was obtained from M.HHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH More MPC for subsequent use For the preparation of EPC 12200819417, the above steps may be repeated, but the methanol was replaced by ethanol (69.0 g '1.5 mole). The EPC corresponding to the last available total of 99.0 g, m.p. 52T, 92% yield. The reaction formula of the embodiment of the present invention is as follows:

(IV) The procedure for further preparing 2,2-bis(4-isocyanatophenyl)propane by MPC or EPC is detailed below.亶MUd~1-6 in addition to phenol-alkane exchange reaction ΜΜΆίζΙ Take 250 ml single-neck round bottom bottle, add MPC (90.6 g, 0.6 m), ΒΡΑ (27.5 g, 〇·ΐ2 mol), methyl Sulfonic acid (28.9 g, 0.3 mol) and magnet. Set up a distillation unit, the reaction temperature is about 90~10 (TC, pressure about 0.1 mmHg, time about 1~2 hours) to distill off the phenol. After the temperature is about 60 ° C, add diethyl ether (about 100 ml) to dilute, After extraction with an aqueous solution of sodium hydroxide (1 N), the organic phase was separated and dried over magnesium sulfate, and then filtered and evaporated to remove ethyl ether under reduced pressure, and then evaporated in vacuo. The excess MPC was distilled off at ~115 ° C. 1 g of the above product was subjected to column chromatography with ethyl acetate and n-hexane as the extract to obtain the product dibasic carbamate 〇.7 g, which was analyzed by 1H NMR. Its structure ' Θ = 1.64 ( s, 6H), 3.67 ( s, 6H), 7.14 7.45 ( dd, 8H, aromatics), 13 200819417 8.55 (s, 2H, -NH), melting point 110~111 ° C, yield Approximately 75%.Example 1-2 The procedure was the same as in Example 1-1 except that the metering and operating conditions of the reactants were as shown in Table 1. Table 1 Example MPC (Molar) BPA (Mohr) A Base sulfonic acid (mole) temperature re) time (hours) yield (%) 1-1 0.6 0.12 0.3 100~125 2~3 75 1-2 0.6 0. 12 0.09 90~100 2~3 40 Example 1-3 Take 250 ml single-neck round bottom bottle, add EPC 12.4 g (0.075 m), BPA 6.9 g (0.03 m), methanesulfonic acid 40.0 g (0.42) Moore) and a magnet. A distillation apparatus was set up, the reaction temperature was about 90 to 100 ° C, the pressure was about 0.1 mmHg, and the time was about 1 hour, and the phenol was distilled off. After the temperature of the solution was lowered to about 60 ° C, the obtained solution was poured into about 1 liter of ice water and stirring was continued for 30 minutes, and the precipitated solid was separated by suction filtration, and then the solid was dissolved by adding ethyl acetate, and After vigorously shaking with a 5% aqueous solution of sodium hydrogencarbonate, the organic phase was separated and dried (MgSO4) and filtered and evaporated. The structure was analyzed by 1H NMR, 5 = L18(t, 6H), 1.63 (s, 6H), 4·06 (q, 4H), 7.13 7·46 (dd, 8H, aromatics), 8·50 (s, 2H, -NH), yield about 60%. 14 200819417 Examples l-4 to l-5 The procedure was the same as in Examples 1-3 except that the amount of methanesulfonic acid used was changed as shown in Table 2. Table 2 Example EPC BPA Methanesulfonic acid temperature time yield (mole) (mole) (mole) (°C) (hours) (%) 1-3 0.075 0.03 0.42 90~100 1 60 1-4 0.075 0.03 0.21 90~100 1 60 1-5 0.075 0.03 0.105 90~100 1 50 Example 1-6 Take 250 ml single neck round bottom bottle, add EPC 33.0 g (0.2 m), BPA 11.4 g (0.05 m) ), concentrated sulfuric acid 54.0 grams (0.55 m) and a magnet. After stirring at 50 ° C for 12 hours under normal pressure, the resulting solution was poured into about 2.2 liters of ice water and stirring was continued for 3 minutes, and the precipitated solid was separated by suction filtration, and then the solid was dissolved by adding ethyl acetate. After vigorously shaking with a 5% aqueous solution of sodium hydrogencarbonate, the organic phase was separated and dried, dried over magnesium sulfate, then filtered and evaporated. The yield was about 40% as analyzed by 1H NMR. It is found from Examples 1-1 to 1-6 that an aromatic compound which can be combined with a monofunctional group, such as methyl hydrazine-phenylcarbamate (MPC), ethyl N-, under the action of an acidic medium. The phenyl carbamate (EPC), after undergoing a transalkylation reaction, replaces the hydrazine on the original BPA to form a dibasic carbamate compound having an Isopropylidene structure. When the ratio of the use of methyl fine acid 15 200819417 is too low, as in the examples 1-2, 1-5, the yield is lower, and the sulfuric acid is selected and the yield is higher under the reaction conditions under normal pressure. Low, as in Example 1_6. Example 2 High Temperature Thermal Cracking Reaction A 500 ml three-necked round bottom flask was charged, and the dibasic carbamate (10 g), diphenyl ether (350 ml) and magnet obtained in the Example were added. A thermometer, Dean-Stark Trap was set up and nitrogen was passed through to remove the methanol produced after the thermal cracking from the reaction, and the reaction was heated to about 250 to 260 ° C for 5 hours. After the temperature of the solution is lowered to below 100 ° C, a large amount of solvent diphenyl ether is removed by vacuum distillation to obtain a white solid 2,2-bis(4-isocyanatophenyl)propane (2,2-bis ( 4-isocyanatophenyl) propane) 6.1 g, yield 75%. The product analysis was as follows: lE NMR 5 δ/= 1.64 (s 5 6 Η) ' 7.08 7·26 ( dd, 8H, aromatics); Elemental analysis: experimental 値C 73.77%, Η 4.80%, 〇11.57%, N 9.91%; Theoretical 値C 73.37%, Η 5.07%, 〇 11.49%, N 10.07%; Melting point: 90~91 °C. It was found from Example 2 that the dibasic carbamate compound can be formed in a high boiling solvent such as diphenyl ether or phenyl cyclohexane via a high temperature thermal cracking reaction 2,2_ Bis(4-isocyanatophenyl)propane and its corresponding methanol or ethanol. After purification, high purity 2,2-bis(4-isocyanatophenyl)propane can be obtained. 16 200819417 Application················ ), heated to 60 ° C, with nitrogen gas in the process. The other 2,2-bis(4-isocyanatophenyl)propane (0.577 g) was dissolved in an appropriate amount of DMAc, added to PTMEG, and then added. Catalytic amount of T9 (about 0.004 g), and warmed to 80 ° C to promote the reaction, mechanically stirred. After 30 minutes as above, add 4,4 > -MDI ( 4.67 g, dissolved in 10 g of toluene The reaction was carried out for 2 hours. Then, the temperature was lowered to 70 ° C, 1,4-BD〇 (1.22 g) was further added, the temperature was raised to 80 ° C, and stirring was continued for 15 hours. Then, about 30 ml of DMF was added to prepare a PU solution. Coated on a Teflon substrate and dried to form a film. Sample No. PU-10 〇mm&i Experimental method as in Application Example 1, except that 2,2-bis(4-isocyanatophenyl)propane isocyanate The molar ratio was increased from 丨〇% to 2〇%, and 4,4 'MDI was reduced from 90% to 80%. The sample number after film formation was PU-20. The control method was as in Application Example 1, except Cyanate part only 4,4 'MDI was used, no addition of 2,2_bis(4-isocyanatophenyl)propane. The sample number after film formation was PU-0. Wake up Wei will form PU-0, PU- for each film. 10. PU_20 polymer, its yellowing resistance is measured in two ways. 17 200819417 1. Place the sample in 7 (TC oven, sample colorimetric at 24, 48, 72 and 96 hours; colorimetric results are shown in the table 3 shows. Table 3 '24 hours 48 hours 72 hours 96 hours PU-0 4-5 3 3 3 PU-10 4-5 3 3 3 PU-20 4 3-4 4 4 2. Place the sample at room temperature It was irradiated with a 30-watt UV lamp (wavelength 254 nm) and sampled at a time of 12, 24, 36 and 48 hours. The results of the colorimetric were divided into 1-5 grades, grade 5 indicates almost colorless and transparent, grade 1 indicates The most severe yellowing discoloration; colorimetric results are shown in Table 4. Table 4 12 hours 24 hours 36 hours 48 hours PU-0 2 1-2 1-2 2 PU-10 3-4 1-2 1-2 1 -2 PU-20 3-4 3-4 3-4 3-4 From Tables 3 and 4, in the 7 (the yellowing test in the TC oven, PU-20 is better, PU-10 and PU-0 are not Significant difference, and at room temperature, the yellowing test irradiated with a 30 watt UV lamp (wavelength 254 nm), after 12 hours of irradiation, ΡΙΜ0, PU-20 It is better than PU-0, and after 48 hours of irradiation, PU-20 still maintains the yellowing resistance of 18 200819417. Therefore, the addition of 2,2-bis(4-isocyanatophenyl)propane to PU polymers has better yellowing resistance and can be used to improve the color change of aromatic PU polymers. 19

Claims (1)

200819417 [Scope of Application] 1. A BPA derivative having a bifunctional group having the following structural formula (III); NHCOOR wherein R is an alkyl group of C1 to C6. 2. The BPA derivative having a difunctional group as described in claim 1, wherein R is a methyl group or an ethyl group. 3. A method of producing a bifunctional BPA derivative having the following structural formula (III); NHCOOR wherein R is a C1 to C6 alkyl group; the method comprises the steps of: (8) a bisphenol A of the formula (I) (4,4^Bisphenol A) and a monofunctional aromatic carbamate of the formula (Π) The compound of the formula (III) is synthesized by subjecting the ester to a phenol-transalkylation reaction in an acidic medium. (1) (Π) 4. The method of claim 3, wherein the molar ratio of the bisphenol a to the monofunctional aromatic urethane in the step (4) is 1: 1 to 1: 10 Good for 1: 2~1: 5. 5. The method of claim 3, wherein the R of the step (4) is methyl 20 200819417 or ethyl. 6. The method according to claim 3, wherein the molar ratio of the bisphenol A to the acidic medium in the step (a) is 1: 1 to 1: 20, preferably 1: 2 to 1: 7 . 7. The method of claim 3, wherein the acidic medium of the step (a) is sulfuric acid (H2S〇4), methanesulfonic acid (CH3S〇3H) or para-toluenesulfonic acid. (p-toluenesulfonic acid). 8. The method of claim 3, wherein the reaction temperature of the step (a) is 40 to 100 ° C, the pressure is 0.1 to 20 mmHg, and the time is 0.5 to 2 hours. 9. A method for producing 2,2-bis(4-isocyanatophenyl)propane by non-phosgene, the 2,2-bis(4-isocyanatophenyl)propane having the following structural formula (IV); OCN NCO (IV) The process comprises the steps of: (8) subjecting a BPA derivative of formula (III) to a high temperature thermal cracking reaction in a high boiling solvent, ROOCHN NHCOOR (III) where R is the hospital base of C1 to C6. 10. The method of claim 9, wherein the R of the BPA derivative of the formula (πΐ) is methyl or ethyl. 11. The method of claim 9, wherein the high boiling point solvent of the step 卬) has a boiling point above 220 °C. The method of claim 9, wherein the high boiling solvent of the step (b) is diphenyl ether or phenyl cyclohexane 〇 13. The method according to the item 9, wherein the concentration of the solution of the formula (b) and the high boiling point solvent is from 3 to 5 wt%. 14. The method of claim 9, wherein the reaction temperature of the step (b) is 220 to 270 °C. 15. The method of claim 9, wherein the reaction time 1 of the step (b) is 1 to 4 hours. 16. The method of claim 9, wherein the product of step (b) is applied to the manufacture of anti-yellowing aromatic polyurethane polyurethanes (PU). 22 200819417 VII. Designated representative map: (1) The representative representative of the case is: (). (2) The symbol of the symbol of this representative figure is simple. Ming: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 200819417 pY / C 7 7 End of the invention patent specification (the format of this manual, Order and bold characters, please do not change any more. ※Please do not fill in the mark. ※Application number: Ρ0chuan ※Application date: ※I PC Classification: I. Name of the invention: (Chinese / English) Non-phosgene manufacturing 2, Method of 2-bis(4-isocyanatophenyl)propane and its intermediates II. Applicant: (1 in total) Name or Name: (Chinese/English) Representative of National Chung Hsing University: (Chinese/English) Xiao Jiefu Address of residence or business office: (Chinese/English) No. 250, Guoguang Road, Taichung City Nationality: (Chinese/English) Republic of China III, Inventor: (5 in total) Name: (Chinese/English) 1-Dai Yuhong 2-Zhong Zihui 3-Lin Xinyou 4-Chen Zhihong5-Chen Weijun Nationality: (Chinese/English) 1-Republic of China 2 - Republic of China 3 - Republic of China 4 - Republic of China 5 - Republic of China 200819417 IV. Statement: □ Claim Patent Law Twelve second paragraph □ □ facts or the provisions of the second paragraph, the fact that the occurrence of said period: years said. □ Apply for patents from the following countries (regions) before applying: [Format please follow: order of acceptance of country (region), application date, application case number] □ There is a claim for patent law Article 27, the first international priority: □ No claim for patent law Article 27, first international priority: □ Advocate patent law Article 29, first domestic priority: [format please: application date, application case number note]] Article 30 of the Patent Law Biomaterials: □ Those who need to deposit biomaterials: Domestic biomaterials [format please note: order of depository, date, number sequence] Foreign biomaterials [format: please register country, institution, date, Number order note] □ Those who do not need to deposit biomaterials: When there is a general knowledge in the technical field that is easy to obtain, no deposit is required. 200819417 IX. Description of the invention: [Technical field of the invention] The present inventors adopt a safer and more environmentally friendly method for producing 2,2-bis(4-isocyanide) in a two-step process from BPA via a urethane precursor. Acid phenyl)propane. [Prior Art] Aromatic isocyanates are chemical materials that are extremely demanding in the market and can be used as raw materials for polyurethane polymers. Among them, TDI and 4,4 'MDI are the most popular. Among them, since 4,4 'MDI has a higher boiling point and a lower toxicity phase, the obtained pu product also has excellent performance', which is preferred by the industry. Currently, the most effective method for producing aromatic or aliphatic isocyanates is the phosgene method, which is a well-known and well-developed technology. The isocyanate is formed by the action of a diamine and phosgene and the initial formation of Carbamic acid, followed by removal of hydrogen chloride. However, the phosgene is dangerous in operation. After the reaction, a large amount of hydrogen chloride is generated, which easily corrodes the reactor and other plant equipment, and is likely to cause environmental pollution. Therefore, the non-phosgene process of isocyanate needs to be developed. The PU polymer made of 4,4 'MDI has a fast reaction speed and excellent mechanical properties. However, after UV light or long-time oxidation, it usually has yellowing phenomenon. The reason is because the hydrogen on the Methylene structure connecting the two benzene rings is easily substituted after UV irradiation or oxidation to generate free radicals, thereby forming a structure of conjugated double bonds between the two benzene rings, resulting in serious The phenomenon of discoloration. 2,2-bis(4-isocyanatophenyl) propane (BCPP) is an aromatic similar chemically similar to 4,4 / -MDI a cyanate compound whose structure is linked by an Isopropylidene structure to 200819417 two isocyanate-containing benzene rings, different from the Methylene structure of 4,4 'MDI, which is attached to the methyl group of the benzene ring. Hydrogen has been replaced by two methyl groups, so it is less susceptible to attack by oxygen or free radicals to form free radicals. Therefore, if a PU polymer is produced by BCPP, the structure of isopropane (IS0pr0pylidene) is less likely to produce a structure having a double bond with two benzene rings under illumination and oxidation, so it is estimated that BCPP can be used to improve 4, 4 'MDI's PU polymer discoloration phenomenon. There are also reports and conclusions in the literature (t. Servay et al., Polymer 41 (2000), 5247-5256). Houser et al., in US Pat. No. 6,063,892, mentions the synthesis of 2,2-bis(4-isocyanatophenyl)propane, but its synthesis is a multi-step synthesis procedure, which is inconvenient and in the process The use of phosgene is the main drawback of this method. The method described above is obtained by alkylating -methyl styrene with benzene, then obtaining 2,2-bis(4-aminophenyl) propane by nitration, hydrogenation, etc., and finally reacting with phosgene. In addition, Sundermann et al. also mentions in US Pat. 4 388 246 that after the carbamate compound is diluted with a solvent, the functional group is thermally cleaved and the alcohol is removed under high temperature reaction conditions to form isocyanic acid. The method of salt. Therefore, the present inventors adopted a safer and more environmentally friendly method of producing 2,2-bis(4-isocyanatophenyl)propane in a two-step process from BPA through a urethane precursor. SUMMARY OF THE INVENTION It is an object of the present invention to provide a bisphenol A (BPA, 4, 4f-Bisphenol A) derivative having a difunctional group which can be used for the manufacture of 2,2-bis(4-isocyanatophenyl)propane. . Another object of the present invention is to provide a method for producing 2,2-bis(4-isocyanatophenyl) propylene from non-phosgene, which has better safety and low pollution, and can be applied to anti-yellowing. Aromatic polyurethane polymer. b 200819417 The bifunctional BPA derivative of the present invention has the following structural formula (III); ROOCHN NHCOOR wherein R is an alkyl group of C1 to C6, preferably a methyl group or an ethyl group. The method for producing a bifunctional BPA derivative of the present invention comprises the steps of: (a) removing phenol-alkylation of BPA of formula (1) and monofunctional aromatic urethane of formula (II) in an acidic medium. (Trans-alkylation) reaction, synthesis of a compound of formula (III); σ (II) NHCOOR The molar ratio of the above bisphenol A (BPA) to the monofunctional aromatic urethane is 1:1 to 1 ··10, preferably 1: 2 to 1: 5; bisphenol The molar ratio of A to the acidic medium is 1: 1 to 1: 20, preferably 1: 2 to 1: 7. The acidic medium is not critical and is preferably sulfuric acid (H2S〇4), methanesulfonic acid (CH3S〇3H) or p-toluenesulfonic acid. Preferred reaction conditions include a temperature of 40 to 100 ° C, a pressure of 0.1 to 20 mmHg, and a time of 5 to 2 hours. The 2,2-bis(4-isocyanatophenyl)propane produced by the non-phosgene process of the present invention has the following structural formula (IV): OCN NCO (IV) The process comprises the steps of: (b) subjecting the anthracene derivative of the above formula (III) to a high temperature thermal cracking reaction in a high boiling solvent. η 200819417 The high boiling point solvent of the above step (b) means that its boiling point is higher than 220 ° C; for example, but not limited to, diphenyl ether, phenyl cyclohexane. The concentration of the solution of the BPA derivative of the formula (III) and the high boiling point solvent is preferably from 3 to 5 wt%. Preferred reaction conditions for the step (b) include a temperature of 220 to 27 CTC for a period of from 1 to 4 hours. The 2,2-bis(4-isocyanatophenyl)propane of the present invention is mainly used for producing an anti-yellowing aromatic polyurethane polymer (PU). [Method for Carrying Out the Invention] The preferred embodiment of the present invention is reacted with methyl N-phenyl carbamate (MPC) or ethyl N-phenyl carbamate (EPC). And the low-cost dihydric phenol BPA is carried out under acidic conditions, and the dibasic carbamate can be directly prepared by removing the phenol and the alkane exchange reaction. In the literature, there are various methods for synthesizing carbamate compounds. For example, Zajacek catalyzes the production of MPC (or EPC) by catalysis of nitrobenzene, methanol (or ethanol) and carbon monoxide with metal selenium (Selenium, Se) in US Pat. 3 895 054. ), Fukuoka produced EPC by catalyzing aniline, ethanol, carbon monoxide and oxygen with palladium (Palladium, Pd) at US Pat. 4 621 149. Our experimental preparation procedure is for the sake of simplicity, using phenyl isocyanate as the starting agent as follows: Take 250 ml three-necked round bottom flask, place magnet and phenyl isocyanate (phenyl Isocyanate) (71.4 g, 0.6 m), and a thermometer and an isobaric separator funnel were placed on the device. Methanol (48.0 g, 1.5 m) was placed in an isocratic separatory funnel, slowly dropped into the reaction flask, and the flask was cooled in an ice bath. After the completion of the methanol instillation (within 60 minutes), stirring was continued for about 1 hour, and an infrared spectrum (IR) was sampled at intervals until the -NC0 absorption peak (2260 ^^1) disappeared, and the reaction was stopped. Excess A. 200819417 The alcohol was concentrated under reduced pressure to give a crude product as a white solid. The crude product obtained was purified by vacuum distillation and then crystallised from n-hexane to afford product 88.0 g, m. In this way, more MPC is prepared for subsequent use. To prepare EPC, the above procedure can be repeated except that methanol is changed to ethanol (69.0 grams, L5 mole). Finally, the corresponding EPC was 99.0 g, the melting point was 52 t, and the yield was 92%. The reaction formula of the embodiment of the present invention is as follows: ch3 Ή ch3 (I) NHCOOR -2PhOH ROOCHN H+/0.1-20 mmHg (Π) CH3 ch3 (III) -NHCOOR 220-270 eC -2ROH OCN-^^· ch3 (IV) -NCO The procedure for the preparation of 2,2-bis(4-isocyanatophenyl)propane by MPC or EPC is detailed below. y Example 1-1~1-6 except phenol-alkane exchange reaction y Example η Take a 250 ml single-neck round bottom bottle, add MPC (90.6 g, 0.6 m), BPA (27.5 g, 0.12 m) Ear), methanesulfonic acid (28.9 g, 0.3 mol) and magnet. A distillation apparatus is set up, the reaction temperature is about 90 to 100 ° C, the pressure is about 0.1 mmHg, and the time is about 1 to 2 hours, and the phenol is distilled off. After the temperature was lowered to about 60 ° C, it was diluted with diethyl ether (about 1 〇〇 200819417 ml), extracted with aqueous sodium hydroxide (IN), and the organic phase was separated and dried over magnesium sulfate, followed by filtration. The solvent diethyl ether was removed by concentration under reduced pressure. Subsequently, excess MPC was distilled off by vacuum distillation at an oil bath temperature of 100 to 115 °C. 1 g of the above product was subjected to column chromatography with ethyl acetate and n-hexane as a solvent to obtain 0.7 g of the product binary carbamate, and its structure was analyzed by 1H NMR (5 = 1.64 (s, 6 Η), 3.67( s,6Η), 7.14 7.45( dd,8Η,aromatics), 8.55 (s,2H,-NH), melting point 110~111°C, yield about 75%. Example 1-2 Example 1-1, except that the metering and operating conditions of the reactants are as shown in Table 1. Table 1 Example MPC (mole) BPA (mole) methanesulfonic acid (mole) temperature (.) Time (hours) Yield (%) 1-1 0.6 0.12 0.3 100~125 2~3 75 1-2 0.6 0.12 .0.09 90-100 2~3 40 Example 250 ml single-neck round bottom bottle was added to EPC 12.4 Gram (0.075 mol), BPA 6.9 g (〇·〇3 molar), methanesulfonic acid 40.0 g (0.42 mol) and a magnet. A distillation unit is set up, the reaction temperature is about 90 to 100 ° C, and the pressure is about 0.1 mmHg, about 1 hour, the phenol was distilled off. After the temperature of the solution dropped to about 60 ° C, the resulting solution was poured into about 1 liter of ice water and stirring was continued for 30 minutes to precipitate the solid. 200819417 The mixture was separated by suction filtration, and the solid was dissolved by ethyl acetate. After vigorously shaking with 5% aqueous sodium hydrogencarbonate solution, the organic phase was separated and dried over magnesium sulfate, then filtered and concentrated under reduced pressure. The structure was analyzed by 1H NMR, 5 = 1.18 (t, 6H), 1.63 (s, 6H), 4·06 (q, 4H), 7.13 7·46 ( dd, 8H, aromatics), 8·50 (s, 2H, _NH), the yield was about 60%. Examples 1-4 to 1-5 The procedure was the same as in Examples 1-3 except that the amount of methanesulfonic acid used was changed as shown in Table 2. Table 2 Examples EPC BPA Methanesulfonic acid temperature time yield (mole) (mole) (mole) (°C) (hours) (%) 1-3 0.075 0.03 0.42 90~100 1 60 1-4 0.075 0.03 0.21 90 ~100 1 60 1-5 0.075 0.03 0.105 90~100 1 50 Example 1-6 Take 250 ml single neck round bottom bottle, add EPC 33.0 g (0.2 mol), BPA 11.4 g (0.05 m), concentrated sulfuric acid 54.0 g (0.55 mol) and a magnet. After stirring at 50 ° C for 12 hours under normal pressure, the resulting solution was poured into about 2.2 liters of ice water and stirring was continued for 30 minutes to precipitate. The solid was separated by suction filtration, and the solid was dissolved by ethyl acetate. After vigorously shaking with 5% aqueous sodium hydrogencarbonate solution, the mixture was separated, and the organic phase was collected, dried over magnesium sulfate, filtered and concentrated under reduced pressure. Solvent. The yield was about 40% as analyzed by 1H NMR. It is found from Examples 1-1 to 1-6 that an aromatic compound such as methyl hydrazine-phenylcarbamate (Mpc) or ethyl N- can be used together with an aromatic medium under the action of an acidic medium. The phenyl carbamate (EPC) forms a dibasic carbamate compound having an Isopropylidene structure after replacing the phenol on the original BPA after undergoing a transalkylation reaction. When the ratio of the amount of methanesulfonic acid used is too low, as in the examples 1-2 and 1-5, the yield is low, and the sulfuric acid is selected and the yield is low under the reaction conditions under normal pressure. As in the example 丨_6. Example 2 High temperature thermal cracking reaction A 500 ml two-necked round bottom flask was charged, and the dibasic carbamate (10 g) of diphenyl ether (350 ml) obtained in Example 1-1 was added. magnet. A thermometer, Dean-Stark Trap was set up and nitrogen was passed through to remove the methanol produced after the thermal cracking from the reaction, and the reaction was heated to about 250 to 260 ° C for 5 hours. After the temperature of the solution is lowered to below 100 ° C, a large amount of solvent diphenyl ether is removed by vacuum distillation to obtain a white solid 2,2-bis(4-isocyanatophenyl)propane (2,2-bis (4- iSocyanatophenyl) propane) 6.1 g, yield 75%. The product analysis was as follows: 4 NMR, 5 = 1.64 (s, 6H), 7.08 7.26 (dd, 8H, aromatics); Elemental analysis · Experimental 値 C 73.77%, Η 4.80%, 0 11.57%, N 9.91%; Theory 値C 73.37%, Η 5.07%, 〇 11.49%, N 10.07%; Melting point: 90-91 ° C. It was found from Example 2 that the dibasic carbamate compound can form a 2,2- via a high temperature thermal cracking reaction in a high boiling solvent such as diphenyl ether or phenyl cyclohexane. Bis(4-isocyanatophenyl)propane and its corresponding 200819417 methanol or ethanol. After purification, high purity 2,2-bis(4-isocyanatophenyl)propane can be obtained. Application: TPU polymer made of 2,2-bis(4-isocyanatophenyl)propane. Example 1 Take a 250 ml separation reaction bottle and add PTMEG (13. 5 g, molecular weight 2,000). Heat to 60 ° C with nitrogen in the process. The other 2,2-bis(4-isocyanatophenyl)propane (0.577 g) was dissolved in an appropriate amount of DMAc, added to PTMEG, and then a catalytic amount of T9 (about 0.004 g) was added, and the temperature was raised to 80. °C promotes the reaction and mechanically stirs it. After 30 minutes as described above, 4,4 'MDI (4.67 g, dissolved in 10 g of toluene) was further added and reacted for 2 hours. Then, the temperature was lowered to 70 ° C, and then 1,4-BD 〇 (1.22 g) was added thereto, and the temperature was raised to 80 ° C, and stirring was continued for 15 hours. Next, about 30 ml of DMF was added to prepare a PU solution, which was coated on a Teflon substrate and dried to form a film, and the sample number was HJ-10. Application Example 2 Experimental method As in Application Example 1, except that the molar ratio of 2,2-bis(4-isocyanatophenyl)propane to isocyanate was increased from 10% to 20%, 4,4 'MDI From 90% to 80%. The sample number after film formation was PU-20. Comparative Example The experimental method was as in Application Example 1, except that the isocyanate portion was only 4,4 'MDI, and no 2,2-bis(4-isocyanatophenyl)propane was added. The sample number after film formation was PU-0. 200819417 Anti-yellowing test The PU-0, PIMO and PU-20 polymers each formed into a film were measured for their yellowing resistance in two ways. 1. Place the sample in 7 (TC oven, sample colorimetric at 24, 48, 72 and 96 hours; colorimetric results are shown in Table 3. Table 3 24 hours 48 hours 72 hours 96 hours PU-0 4- 5 3 3 3 PU-10 4-5 3 3 3 PU-20 4 3-4 4 4 2. The sample is irradiated with a 30 watt UV lamp (wavelength 254 nm) at room temperature, at time 12, 24, The colorimetric results were sampled at 36 and 48 hours. The results of the colorimetric were divided into 1-5 grades. Grade 5 indicates almost colorless and transparent, and grade 1 indicates the most severe yellowing discoloration. The colorimetric results are shown in Table 4. Table 4 12 hours 24 hours 36 hours 48 hours PU-0 2 1-2 1-2 2 PU-10 3-4 1-2 1-2 1-2 PU-20 3-4 3-4 3-4 3-4 200819417 3, 4, in the 70 ° C oven yellowing test, PU-20 is better, PIM0 and PU-0 no significant difference, and at room temperature, with 30 watt UV lamp (wavelength 254 nm) The yellowing test showed that PU-10 and PU-20 were significantly better than PIM after 12 hours of irradiation, and PU-20 maintained better yellowing resistance after 48 hours of irradiation. Therefore, the addition of 2,2-bis(4-isocyanatophenyl)propane to PU polymers has better yellowing resistance and can be used to improve the color change of aromatic PU polymers. 200819417, V. Chinese Abstract: The present invention provides a method for producing 2,2-bis(4-isocyanatophenyl)propane from non-phosgene, which is composed of bisphenol A (BPA) in an acidic medium, In the phenol a, the phenol released by the bond is transalkylated with the aromatic carbamate, and the phenol exchanged in the process is gradually removed from the reaction by a reduced pressure operation to promote the alkane exchange. The acceleration and completion of the reaction eventually results in the formation of the main product binary carbamate. The dibasic carbamate can be further subjected to a high temperature thermal cracking reaction in a high boiling solvent to form 2,2-bis(4-isocyanatophenyl)propane, and is used for producing an anti-yellowing aromatic polyurethane. Polyurethanes (PU). 6. Abstract of the Invention: 200819417 [Scope of Application] 1. A BPA derivative having a difunctional group having the following structural formula (III); ROOCHN NHCOOR (ra) wherein R is an alkyl group of C1 to C6. 2. A BPA derivative having a difunctional group as described in claim 1, wherein R is a methyl group or an ethyl group. 3. A process for producing a bifunctional BPA derivative having the following structural formula (III); ROOCHN NHCOOR (ΠΙ) wherein R is an alkyl group of Cl~C6; the method comprises the steps of: (8) making a bisphenol A of the formula (I) (4,4f-Bisphenol A) and a monofunctional aromatic group of the formula (II) The carbamate is subjected to a trans-alkylation reaction in an acidic medium to synthesize a compound of the formula (III). The method of claim 3, wherein the molar ratio of the bisphenol A to the monofunctional aromatic urethane in the step (a) is 1: 1 to 1 · 1 〇, Preferably, the method of claim 3, wherein R of the step (a) is methyl 200819417 or ethyl. 6. The method of claim 3, wherein the molar ratio of the biguanide A to the acidic medium in the step (a) is 1: 1 to 1: 20, preferably 1: 2 to 1 · 7. 7. The method of claim 3, wherein the acidic medium of the step (8) is sulfuric acid (H2S〇4), methanesulfonic acid (CHsSChH) or p-toluenesulfonic acid (p-toluenesulfonic acid). Acid). 8. The method of claim 3, wherein the reaction temperature of the step (a) is 40 to 10 ° C, the pressure is 0.1 to 20 mmHg, and the time is 0.5 to 2 hours. 9. A method for producing 2,2-bis(4-isocyanatophenyl)propane by non-phosgene, the 2,2-bis(4-isocyanatophenyl)propane having the following structural formula (IV); OCN NCO (IV) The process comprises the steps of: (b) subjecting the BPA derivative of formula (III) to a high temperature thermal cracking reaction in a high boiling solvent, ROOCHN NHCOOR (III) wherein R is an alkyl group of C1 to C6. 10. The method of claim 9, wherein the R of the BPA derivative of the formula (in) is methyl or ethyl. 11. The method of claim 9, wherein the high boiling point solvent of the step (8) has a boiling point higher than 22 (TC). The method of claim 9, wherein the step ( b) The high boiling point solvent is diphenyl ether or phenyl cyclohexane. The method according to claim 9, wherein the step (b) is the formula (III) The concentration of the solution of the BPA derivative and the high-boiling solvent is from 3 to 5 wt%. The method of claim 9, wherein the reaction temperature of the step (b) is 220 to 270 °C. U. The method of claim 9, wherein the reaction time of the step (b) is from 1 to 4 hours. The method of claim 9 wherein the product of the step (b) It is applied to the manufacture of anti-yellowing aromatic polyesters (PU). 200819417 VII. Designation of representative drawings: (1) The representative representative of the case is: () (II) The symbol of the representative figure Brief Description: 8. If there is a chemical formula in this case, please reveal the best Chemical Formula invention illustrating features: ROOCHN -NHCOOR (III)