TW426661B - Halogen-containing high-carbon alcohol for plasticizer and method for producing the same - Google Patents

Abstract

This invention discloses halogen-containing high-carbon alcohols for a plasticizer and esters of the same. The plasticizer of this invention has advantages of excellently low volatility, compatibility and low temperature property. The halogen-containing high-carbon alcohols are produced by using a Α-olefin as starting material, then proceeding hydrogen-added formylation, aldehyde-added condensation, halogenation, and hydrogenation to get the halogen-containing alcohols. Afer estifying the the halogen-containing alcohols, the halogen-containing esters are produced.

Description

42666 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (1) (1) Field of the Invention The present invention relates to a novel alcohol containing high carbon number and its esters, and the alcohol and Method for preparing esters The halogen-containing alcohols and esters of the present invention can be applied to plasticizers (especially plasticizers of polyvinyl chloride) and the like, and have the advantages of low volatility, compatibility, and low-temperature properties. Background alcohols used in plasticizers commonly used in the industry are 2-ethylhexanol (2-EH), isononyl alcohol (INA), and isodecanol (IDA). Acid®f or adipic acid reacts to make plasticizers for PVC, such as dop, DINP, DINA, DIPP, DIDA, etc., which can be used in toys, wires and cables, meat packaging, automotive interior materials and lubricants, etc. U.S. Patent No. 2,921,038 discloses a method for synthesizing ten carbon alcohols (2-propyl-1-heptanol), comprising reacting n-butyl alcohol with carbon monoxide and hydrogen to form a rhodium or cobalt-containing chloride The catalyst catalyzes the production of n-valeraldehyde. Two molecules of n-valeraldehyde are obtained through the aldehyde addition condensation reaction to obtain 2-propane. 2-heptenal, followed by hydrogenation to obtain 2-propyl-1-heptanol (2-PH), and finally 2-PH reacts with dianhydride to obtain esters (DPHP), which can be applied to Plasticizer. European Patent No. 094456 discloses a method for converting a mixed isomer of butenes into a plasticizer alcohol of ten carbons. 'This method includes the use of oxygenation of butenes (〇χ〇) to obtain at least about 66 % N-valeraldehyde, and then under the condition that n-valeraldehyde and isovaleraldehyde do not undergo cross-addition acid condensation reaction, the aldehydes are added to formaldehyde condensation reaction, and then the hydrogenation reaction is performed to obtain at least 80 ~ 90% 2 -Ten carbon alcohols of propylheptanol. The advantage of this method is that it is not necessary to separate the difficult to separate aldehyde isomers before the aldehyde condensation reaction, and it can produce high yield and excellent plasticity in a highly efficient process. "Alcohols" 2850178B This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3.! 〇, 〇〇〇 --------- L :. Packing ----- -Order ------ '(Please read the note on the back before filling in this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 266 6 1 β Α7 ____ B7 V. Description of the Invention (2) European Patent No. 0366089 discloses a clcj alcohol mixture for plasticizer and a preparation method thereof. The C1 () alcohol mixture includes L-propylheptanol and has n-pentyl alcohol. An alcohol having a condensation product structure of an acid and 2-methylbutanoic acid, an alcohol having a structure of a condensation product of n-methylenealdehyde and 3-methylbutyraldehyde, an alcohol having a structure of a condensation product of n-methylenealdehyde and a specific acid, and Other c1Q alcohols. The preparation method of the Ci0 alcohols mixture includes a hydroformylation reaction, an aldehyde condensation reaction, and a hydrogenation reaction for Q-homing hydrocarbons. The alcohols thus prepared are mainly used as starting materials for plasticizers for the production of gas vinyl resins. When the vinegars obtained by further esterification of the above-mentioned Clc alcohol mixture with carboxylic acid are applied to the plasticizer of polyethylene gas, they are better than di (2-ethylhexyl) ester (Doop) plasticizer and Diisodecyl acid (DIDP) plasticizer has a higher modulus and electrical resistivity of 100% and lower evaporation loss. The present invention is to provide a plasticizer with better low volatility, compatibility and low temperature characteristics by introducing halogen into the molecule. (3) Summary of the Invention The present invention relates to a compound of the following formula (I) and its esters: CH3 — (CH2) n — CHX — CR ^ — CH2OH (I) (where η is an integer of 0 to 3; X and X 'may be the same as or different from each other and each is a halogen; R is C3 to alkynyl)' The compound of formula (I) and its vinegar may be used as a plasticizer, especially a plasticizer of polyvinyl chloride. The present invention also relates to a method for manufacturing the compound of the formula (I) and its esters, which comprises using lower alpha-hydrocarbons as raw materials, hydroformylation reaction, aldehyde condensation reaction, curing reaction and nitriding reaction. . —4 — (Amendment page)-^ ιτττΓττττ ^ πσυ ......... 1 ----- _ This paper size adopts China National Standard (CNS) Α4 specification (210X297 mm) -1— —— It, equipment — IIII order I line (please read the precautions on the back before filling out this page) 426661 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 --------- B7__ 5. Description of the invention ( 3) (4) Detailed description of the invention The method for synthesizing the novel halogen-containing high carbon number plasticizer of the present invention includes the use of lower alpha-olefins such as propylene and 1-butyrate as raw materials, and-carbon oxide and hydrogen Hydroformylation reaction to obtain aldehydes, and then the aldehydes are subjected to condensation reaction in alkaline solution to obtain alkenyl; this alkenal is reacted with # prime, and then hydrogenated to obtain high carbon number alcohol The esters obtained by further esterification of this alcohol are excellent plasticizers. After the plasticizer synthesized by the present invention is blended with PVC, the plasticity is better than the conventional DOP plasticizer. In detail, the halogen-containing high carbon number alcohol used for the plasticizer synthesized in the present invention is a compound represented by the following formula (I): CH3-(CH2) n-CHX-CRX *-CH2OH (I) where, n is an integer of 0 to 3, X and X are each halogen such as fluorine, gas, bromine, iodine, and R is a C3 to C6 alkyl group. In the process of synthesizing high-carbon alcohols containing nansin according to the present invention, the hydroformylation reaction can use RhH (CO) (PPh3) 3 / PPI13 compounds as catalysts. The preferred reaction temperature is 80 ~ 150 ° C. The reaction was carried out under the pressure of 100-BOOpsig CO / H2 to obtain aldehydes. The aldehydes thus obtained are a mixture of linear aldehydes and branched aldehydes, and the ratio of linear aldehydes to branched aldehydes (n-aldehyde to isoaldehyde) is about 3: 1 ~ 15: 1. Some of the aldehydes without branching can be directly subjected to aldehyde addition condensation reaction. The aldehyde-addition condensation reaction is performed in an alkaline solution, preferably a 2-10% alkaline aqueous solution such as sodium hydroxide or potassium hydroxide solution, and the reaction temperature is controlled between 60 and 150. It is 90 to 98%. For example, using propylene or 1-butene as a starting material, 2-ethyl-2-hexenal or 2-propyl-2 can be obtained in a yield of 90 to 98% after an aldehyde addition condensation reaction. Heptenal. Then, the enal obtained by the above reaction is subjected to a low-temperature and matt reaction, and the yield of the obtained product is about 80 to 90%. The low thirst condition of the chemical reaction is preferably -5 ° C; if the gasification reaction is performed, the product is pale yellow. (Please read the note on the back before filling in this page.) -------- Order --- — 5 — (Amendment page) -28707016.dQg- This paper size applies to Chinese national standards (CNS > Μ specifications ( 21〇 > < 297 mm〉. 溆 ---------------- 4 266 6 1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 —— _____ B7 V. Invention Note (4) The product obtained by the above-mentioned southerization reaction is then subjected to a hydrogenation reaction to obtain a halogen-containing high carbon number alcohol with a yield of more than 90%. For example, propylene or 1-butene is used as a raw material, The obtained product is 2-ethyl-2,3-dichloro-1-hexanol or 2-propyl ~ 2,3-digas-1-heptanol (where the #chemical reaction is a chlorination reaction). This hydrogenation The reaction can be accelerated by Cu / Zn catalyst or Raney Ni or other reducing agents such as NaBH4. Among them, the hydrogenation reaction rate using NaBH4 as the reducing agent is the fastest. A functional organic acid such as a cationic acid or adipic acid is further subjected to esterification to obtain esters. This esterification reaction can be performed at a temperature of 90 ~ 150 ° C using sulfuric acid as a catalyst. The above-mentioned halogen-containing high alcohols It can also be reacted with phttialoylchloride, using tiger as a catalyst to obtain an ester plasticizer (DCOP or DCPHP) with a yield of about 90% to 95%. The ester plasticizer of the present invention and PVC The test piece obtained by blending and compression molding was measured by two methods of ASTM (American Society for Testing Materials) D638 and D257, respectively, for measuring the loo% modulus and resistivity of the test piece, which proves that the plasticizer (DCPHP) comparison of the present invention It is known that the plasticizer (Doop, DPHP) has a higher 10000/0 modulus and resistivity. The present invention will be further described by examples below, but the present invention is by no means limited to these examples. Five) Examples Example 1: Synthesis of 1-butyraldehyde 500 ml of ethanol containing 100 ppm RhH (CO) (PPh3) 3 and 0.01 Moore PPh3 was added to a human pressure limb scarf, followed by αιmol The ear-cuffed woman and 400 psig of Hs / CO mixed gas (H2 / co = 1: 1) were passed into the reactor, and the reaction was carried out at 1CKTC for 2 hours to obtain colorless and transparent butyric acid.

2850178B (Please read the note on the back before filling this page) --ο- 装., 11

L This paper size applies to China National Standards (CNS) A4 specifications (210 x 297 feet) 83. 3.10,000 4 266 6 1, A7 B7 V. Description of the invention (and Example 2: Synthesis and implementation of 1-valeraldehyde) The reaction was carried out in the same manner as in Example 1, but 1-butene was substituted for propylamidine to obtain a colorless and transparent 1-cene. Example 3: Synthesis of 2-ethyl-2-hexenal 100 g of 3 wt% NaOH The aqueous solution was heated to 95 ° C, and then 100 g of butyraldehyde was slowly added to the aqueous NaOH solution, and the reaction was continued for 3 hours while maintaining the temperature at 95 T. After cooling, the organic layer and the aqueous layer were separated, and the organic layer was purified by distillation under reduced pressure. The product 2-ethyl ~ 2 * • associate was obtained with a yield of 95%. Example 4: Synthesis of 2-propyl-2-heptenal was reacted in the same manner as in Example 3, but with 1 -Butyric acid substituted with butyric acid 'to get 2-propyl-2-heptan, the yield is about 95%. (Please read the precautions on the back before filling this page)

Printed in Example 5 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs: Synthesis of 2-ethyl-2,3-dichlorohexanal In 0.3 ml of dichloromethane solvent was added 0.3 mole of 2-ethyl-2- The wife passed in chlorine gas (flow rate 10 ml / min) at 0 ° C and in the absence of light. After 6 hours of reaction, the dichloromethane solvent was removed and distilled under reduced pressure to give the pale yellow product 2-ethyl -2,3-Digashexanal, yield 85%. Example 6: Synthesis of 2-propyl-2,3-dichloroheptanal The reaction was performed in the same manner as in Example 5, but 2-ethyl-2-heptenal was substituted for 2-ethyl-2- Hexenal to give the product 2-propyl-2,3-dichloroheptanal in a yield of about 87%. Example 7: Synthesis of 2-ethyl-2,3-digas-1-hexanol 0.2 ml of 2-ethyl-2,3-dichlorohexanal was added to 50 ml of methanol, and the solution was cooled to After 0 ° C, 02 moles of NaBH4 was added slowly, and the reaction was allowed to proceed at 0 ° C for 2.5 hours. Then, 30 ml of ice water was added, and the product was extracted with 30 ml of ethyl acetate. The product was distilled under reduced pressure to obtain the product 2-ethyl-2,3-dichloro-1-hexanol with a yield of 94%. —7 a

2850178B Standard size country _ Township (⑽) (2 seems to be 297 Gongchu) 83.3.10,000 42866 1 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -8 5. Description of the invention (e) Example 8-2 The synthesis of propyl-2,3-dichloro-1-heptanol was carried out in the same manner as in Example 7, except that 2-ethyl-2,3-dichloroheptanoic acid was substituted with 2-propyl-2,3-dichloroheptanoic acid. 3-Dichlorohexanal to give the product 2-propyl-2,3-dichloro-1-heptanol with a yield of about 95%. The spectral data of this product are as follows. 'HNMR (200MHz, CDCIa): δ 0.92 (m), 1.26-2.07 (m), 2.73 (br), 3.81 (dt), 4.05 (d), 4.21 (d) ppm FT-IR: 3376, 2963, 2934 , 2874, 1468, 1381, 1059, 635cm1 FABMS (m-1): 225, 227 Example 9: Synthesis of bis (2-ethyl-2,3-dichloro-1-hexyl) ester (DCOP) 0,3 mole of 2-ethyl-2,3-digas-1-hexanol was reacted with 0.3 mole of terephthalic anhydride in 50 ml of toluene. After adding sulfuric acid as a catalyst, the reaction was refluxed for 24 hours. Hours, the product DC0P was obtained by distillation with a yield of 90%. Example 10: Synthesis of phthalic acid bis (2-ethyl_2,3-dichloro-1-hexyl) vinegar to make 50 grams of 2-ethyl-2 , 3-Dichloro-1-hexanol was dissolved in 30 ml of ether, and "• pyridine was used as a catalyst, and then 15 ml of chlorinated chlorine was slowly added to reflux the reaction for 16 hours, and then washed with water to remove salts and pyridine. The organic layer was further subjected to distillation under reduced pressure to obtain the product DCOP with a yield of 90%. Example 11: Synthesis of acid bis (2-propyl-2,3-dichloro-1-heptyl) ester (DCPHP) The reaction was performed in the same manner as in Example 9 or 10, but with 2-propyl _ 2,3-dichloro-1-heptanol was substituted for 2-ethyl-2,3-digas-1-hexanol to obtain the product DCPHP. The spectral data of this product are shown below.

2850178B This paper uses China National Standards (CNS > A4 size (2 丨 0X297) 297 81 3.10,000 .—II Order—— I —I—'iv (Please read the notes on the back before filling in this Page). 4 266 6 1 ^ Α7 Β7 V. Description of the invention (i) 'HNMR (200MHz, CDC13): δ 0.96 (m), 1.33-2.12 (m), 4.09 (dd), 4.23 (dd), 4.65 ( s), 7.57 (m), 7.75 (m) ppm FT-IR: 2983, 2934, 2874, 1736, 1466, 1276, 1072, 734cm1 Example 12: Blend the esters obtained in Example 11 with PVC (40 RPH, that is, 40 parts by weight of plasticizer and 60 parts by weight of PVC), and then press-molded to obtain test pieces. The two methods of ASTM D638 and D257 were used to measure the 100/0 modulus (kg / cm2) and resistivity of the test pieces. (Ω / cm), and compared with the conventional plasticizers DOP and DPHP, the results are as follows: -------- ^ r equipment— < Please read the precautions on the back before filling this page) DOP DPHP DCPHP 100% Modulus (kg / cm2) 212 240 285 Resistivity (X 1012 Ω / cm) 69 70 317 Ordered by the Central Standards Bureau of the Ministry of Economic Affairs and the Consumer Cooperative Printed Bags The above results prove that the DCPHP of the present invention is better than conventional Plasticizers DOP and DPHP have higher 100% modulus and resistivity.

2850178B 83. 3. 10,000 This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 OX29? Mm)

Claims (1)

Α8 Bi? C8 D8 VI. Patent Application Target No. 85102716 Patent Application Patent Amendment 1. A plasticizer compound of the following formula (I) and its esters CH3-(CH2) n _ CHX -CRX- CH2OH (where n is an integer from 0 to 3; X is chlorine; R is C6 and C6). 2. For example, the compound and its acid esters of item 1 in the application scope, wherein η is 1. 3. For example, the compound and its acid esters in item 1 of the patent application scope, wherein η is 2. 4. The compound and its acid esters according to item 1 of the application, wherein R is propyl. 5. For example, the compound and its acid brewing compounds in item 1 of the patent application scope, wherein R is butyl. 6. If the compound and its acid esters in item 1 of the scope of patent application are used, they can be used as plasticizers for polyethylene. < Please read the notes on the back before filling this page) Printed media of the Central Tezawa Sumi Masako Consumer Cooperative—1— (89.12.11 revised page) I8912-85102716.doc. ^^^^^ National Standard (0) 8 specifications (21 (^ 297 mm) ) Announcement Thai application date SS ^ U Case No. g 5 1 0 z 9 1 ^ Category. (The above are filled in by the Bureau) A4 C4 426661 Printed by the Central Standards Bureau of the Ministry of Economic Affairs f | Patent Specification-, = Name Creation of Chinese plasticizers containing halogen-containing high carbon number alcohols and its 1 production method miiBiii English 'Halogen-containing high-carbon alcohol lor plasticizer and metnod for producing the same name Wang Xianzhi, Chen Yijun, Zhan Shuhua, invention, (National borrowing) Republic of China Residence and residence No. 321, Section 2, Guangfu Road, Hsinchu City Name (name) Box head (prisoner) Industrial Research Institute of the Republic of China III. Applicant's residence, residence (office) Hsinchu County Representative name Lin Xinyi No. 195, Section 4, Zhongxing Road, Zhudong Town Lin Xinyi-1 _ Γ89.12.11 ^ .1: ΐΓ'ΐ (Please read the precautions on the back before filling in the blocks on this page) A 4 (210X297 Gong) 78. 8. 3,000 Α8 Bi? C8 D8 VI. Patent Application Target No. 85102716 Patent Application Patent Amendment 1. A plasticizer compound of the following formula (I) and its esters CH3-(CH2) n _ CHX -CRX-CH2OH (where n is an integer from 0 to 3; X is chlorine; R is C6 and C6). 2. For example, the compound and its acid esters of item 1 in the scope of patent application, where η is 1 3. For example, the compound and its acid esters of item 1 in the scope of the patent application, where η is 2. 4. · For the compound and the acid esters of the item 1, in scope of the patent application, where R is propyl. 5. As the application The compounds in the scope of the patent No. 1 and their acid brews, where R is butyl. 6. If the compounds in the scope of the patent are No. 1 and their acid esters, they can be used as plasticizers for polyethylene. ≪ Please first (Read the notes on the back and fill out this page) Printed media of the Central Tezawa Sumi Masako Consumer Cooperative—1— (89.12.11 revised page) I8912-85102716.doc. ^^^^^ National Standard (0) 8 specifications (21 (^ 297 mm) )