TW486493B - Propanediol derivative and process for preparing copolyester using said propanediol derivative as comonomer - Google Patents

Abstract

The present invention relates to a propanediol derivative and a process for preparing a copolyester using the propanediol derivative as the comonomer. The present invention employs a novel propanediol derivative to replace the conventional NPG. The process for preparing the copolyester includes two steps. The first step is an esterification reaction, which involves reacting a first phthalic acid or its ester with a first alkyl diol to form an oligomer of bis(hydroxyalkyl) benzendicarboxylate. The second step is a copolymerization reaction, which involves reacting the oligomer and the propanediol derivative of the present invention to form the copolyester.

Description

486493 V. Description of the invention (1) ^-The present invention relates to a method for preparing a copolyester, and more particularly to a method for preparing a copolymer S by a two-step synthesis method using the propylene glycol derivative of the present invention as a comonomer. Polyester copolymer is a widely used raw material for making shrinkable resins, films and fibers. For example, U.S. Paten Co. 53841 84, 54881 23, and 538081 6 are copolyesters, which are used for shrinkable and easily dyeable resins / fibers or applied to coatings. JP-A-Sho, 0 6 2 8 0 1 1 4, 0 5 1 6 3 3 3 4 and 0 5 0 5 2 1 2 use copolyesters as high-shrinkage fibers or high-speed spinning raw materials. α »At present, there are two methods for synthesizing the copolyester of polyethylene terephthalate (PET), which are generally known in the art: (1) One-step synthesis method (in the esterification reaction) Adding co-monomers in the stage) Terephthalic acid + ethylene glycol + co-monomers-copolyester (2) Two-step synthesis method (adding co-monomers in the polymerization reaction stage) Esterification reaction: terephthalic acid + ethyl Polymerization reaction of diol> PET polyester: oligomer of PET polyester + comonomer-copolyester The above-mentioned one-step synthesis method, as disclosed in US Patent 53841 84, 5488 1 23 and 538081 6. The steps are as follows: benzenedicarboxylic acid, ethylene glycol (EG), and comonomer (a diol) are added to the reaction tank to perform an esterification reaction. After the completion of the esterification reaction, the temperature and pressure are reduced again to perform a polymerization reaction to obtain a copolyester. Generally speaking, one-step synthesis is suitable for low boiling points or poor reactivity.

Page 6 486493 V. Comonomers of the invention description (2), such as 2,2-dimethyl-1,3-propanediol (2,2-dimethyl-1,3-propanediol; neopentyl glycol;

(Hereinafter referred to as NPG). The disadvantage is that if the synthesis of other copolyesters is to be changed, it is necessary to clean the esterification tank and the polymerization tank to reduce the economics of diversification in a small amount. In addition, it is not easy to obtain an excellent random copolyester. < To obtain a better mixed-co-polyester, Yu Shuzhi's two-step synthesis method is generally used. The reaction is divided into two stages: esterification reaction and polymerization reaction. Phthalic acid and ethylene glycol first react to form a PET polyester polymer (esterification reaction), and then the PET polyester oligomer and comonomer The polymerization reaction forms a copolymerized vinegar (polymerization, polymerization). As disclosed in U.S. Patent Nos. 5,553,907, 5,549,094, and 5 6 1 2 4 2 3. Based on modified aromatic dibasic acid as comonomer, it is added to PET oligomer [BHET; bis (2-hydroxyethyl) terephthalate; A better mixed-row copolyester was obtained.

In addition to obtaining better blended copolyesters, one of the advantages of using the two-step synthesis method is that it can improve the economics of small-scale and diversified production in the factory. The reason is that when a comonomer is added in the polymerization reaction stage, the step of cleaning the esterification tank and the polymerization tank after the reaction can be omitted. However, it is more difficult for certain low-boiling comonomers, such as NPG or 1,3 ~ propylene glycol compounds. Because this = glycol has a lower boiling point, and its reactivity with βΗET is also lower, at 3 k a% reaction, each is easily detached. Therefore, the content of unreacted NPG or 1′3 glycerol compounds in ethylene glycol is increased, so that the recovery of ethylene glycol is more based on the reasons mentioned above. When using low boiling point comonomers (such as NPG) to prepare

486493 V. Description of the invention (3) In the case of PET copolyesters containing comonomers, the above-mentioned one-step synthesis method is used in the current technology, so it has the following disadvantages. (1) Copolyester with better miscibility cannot be obtained. (2) The content of NPG reaction in the copolyester is often lower than the theoretical amount added before NPG reaction. That is, the reaction amount of NPG added is not ideal. (3) The content of N P G in the copolymerized S purpose product is unstable, which is likely to change with changes in reaction conditions and conditions, affecting subsequent processing processes and product quality. (4) The medium in which the ethylene glycol (EG) is steamed in the reaction contains a high amount of NPG, which increases the difficulty and cost of recovering ethylene glycol. (5) The melting point of NPG is relatively low, and there is often a phenomenon of sticking to each other 'to increase the difficulty of the operation of the factory to add solid materials. Therefore, the object of the present invention is to provide an improved method for preparing copolymerization to solve the above-mentioned shortcomings. A newly synthesized propylene glycol derivative is used instead of the conventionally used NPG, so that it can be used in a two-step synthesis to produce a copolyester. In this way, better co-polyesters can be obtained. The content of NPG in the copolymerization can be greatly improved. The reduction of the amount of NPG can make it easier to recover the ethylene glycol. Moreover, the content of NPG in the copolyester is stable and it is not easy to change with the change of process conditions. Subsequent processing processes and products have a positive impact. In addition, the newly synthesized NPG derivatives do not have the problem of sticking to each other, so it is easier to feed them in a solid manner, reducing plant operation problems. In addition, the newly synthesized NPG derivative can be carried out using the raw materials and equipment of existing manufacturers. In order to achieve the purpose of the present invention, the propylene glycol derivative of the present invention has the following chemical formula (I): 486493 V. Description of the invention (4) HO— (CH2) p- (

CH21

-CH2-0

'. -(CH2) q—OH (I) where «R1 and R2 can be the same or different and are H, CrC8 alkyl,-(ch2) SX, where X is optional F, c 1, Br, I, N In the group formed by 〇3, s is an integer of 1 to 5; and P and q may be the same or different and are integers of 2 to 8. The method for preparing a copolyester according to the present invention includes the following steps: (a) reacting a first phthalic acid or an ester thereof with a first alkyl diol to obtain a dibasic acid ester of phthalic acid [ bi S (hydr〇Xy a ^ ky 1) benzenedicarboxylate] oligomer; and (b) copolymerize the oligomer with a propylene glycol derivative other than the chemical formula (j) described in item 1 of the scope of patent application The reaction to obtain the copolymer according to the present invention is a good example: R1 and! ^ 2 groups' P and q are both 2. The comparison of the propylene glycol derivatives represented by the chemical formula (I) is (^ -〇8alkynyl. Specific examples are: ri and r2 are both methyl

The obtained propylene glycol derivative can be prepared into vinegars by the following steps, and esterified with the propylene glycol compound of C's second benzene m, and the dihydric monodiol: R1 H0-CH2-C ^ CH2 -〇H (||) R2

5. Explanation of the invention (5), in which R1 and R2 can be the same or different, and are H, Ci_C8, and s', where X is a family composed of optional F, C1, Br, 丨, and No3. : Integer to 5. It is better to be dagger-. 8 烧 基。 8 burning base. When… and, di-, the propylene glycol compound of formula (II) is 2, 2-difluorenyl to i 3: forma (NPG). Tripropylene glycol The first phthalic acid or its esters used in the present invention may be the same as or different from the second acid or its esters. Specific examples include paraben; formic acid, metabendicarboxylic acid, phthalic acid, Biphenyldicarboxylic acid, naphthalenecyclodicarboxylic acid, and esters thereof. According to the following specific embodiments of the present invention, the following: The acid or its essential species is terephthalic acid. Second phthalic acid or its vinegar = dimethyl dicarboxylate (DMT). The first alkyl diol and the second alkyl diol used in the present invention may be the same or different, and the number of carbons thereof is preferably between 2 and 8. 2. In the above step (a), when the first phthalic acid or its purpose is terephthalic acid and the first alkyl diol is ethylene glycol, the benzene diester obtained is esterified. The oligomeric polymer of dihydroxyalkyl oxalate is PET polymer-bis (2-hydroxyethyl terephthalate) [bis (2-hydroxy ethyl) terephthalate); BHET for short. The method of the present invention is a one-step reaction: i reaction and polymerization. The acetic acid reaction is preferably at a temperature of 180 ° C. (: Up to 250 t :, and preferably in the presence of a catalyst. Specific examples of esterification catalysts include tetrapropyl titanium, tetrabutyl titanium, calcium acetate, zinc acetate, and manganese acetate. In the composition group, the copolymerization reaction is preferably performed at a temperature of 250 ° C to 280 ° C and a pressure of 2 to 0.1 Torr. Moreover, it is preferably performed in the presence of a polymerization catalyst. Polymerization 486493 V. Invention Note (6) Specific examples of catalysts include: tetrapropyl titanium, tetrabutyl titanium, dioxane, antimony cool acid, diethanol antimony, cobalt acetate, and tin acetate: among the group. Titanium and tetrabutyl titanium can be used as esterification catalyst and polymerization catalyst at the same time. In addition, the copolymerization reaction is preferably performed in the presence of an additive, which can be selected from trimethyl phosphorus and triphenyl phosphorus. Or antioxidants. To make the purpose and method of the present invention clearer, the present invention will be illustrated by the following examples, but the scope of the present invention is not limited. The & The range shall prevail. Example 1: Synthesis of Propylene Glycol Derivatives (Modified NPG) Reactants were added to a 2 liter stainless steel reaction tank with a fractionation tube, a stirring device, and an oxygen inlet: NPG (32 g, 0.3 mol), dimethyl terephthalate (DMT) ( 300 grams, 1.5 moles), catalyst (tetraisopropyl titanium) (0.3 grams), heated from room temperature to 190 ° C, esterification reaction, at this time methanol was distilled off one after the other. When methanol is no longer distilled off, the temperature is reduced to below 150 ° C, and the pressure is slowly reduced to extract unreacted dimethyl terephthalate and unreacted NPG from the reaction solution. At this time, return to normal pressure. From this stainless steel reaction tank, take a small amount of product (Compound A) for H1 NMR spectral analysis: H1 NMR (CF3COOD): 7. 5 (4H, phenyl), 3. 8 (2H, OCH2) , 3.4 (3H, OCH3), 0.7 (3H, CH3) (ppm) The chemical formula of compound A is:

Page 11 486493 V. Description of the invention (7) After taking a small amount of product, add an excess of ethylene glycol (115 grams, 1.8 moles) to this stainless steel reaction tank [if necessary, add Catalyst acetic acid (0.2 g)] 'Heated to 220 C' When the Sf · is no longer distilled out, slowly depressurize and distill excess ethylene glycol. After the compound remaining in the reactor was quenched with hot water, 10 times the volume of methanol was slowly added dropwise. This precipitate (that is, compound B. Take a small amount of product for spectral analysis: H1 NMR (CF3COOD): 7. 6-7. 5 (4H, phenyl), 4 · 3-4 · 1 (3H, hydroxyethyl), 3 · 8 (2H, OCH2, NPG), 3.8 (0CH2), 0 · 7-0.5 (CH3, NPG) (ppm).

Compound B: [2,2-dimethyl-1,3-propanediol-bis (2-hydroxyethanecarbonyl-4-benzoate)] [2,2-dimethyl-1,3-propanediol-bis ( The chemical formula of 2-hydroxyl-ethy loxycarbony 1 -4-benzoate) is:

HOCH2CH2O-C

~ 〇 ~ C-OCH2CH2OH (B) Melting point is 1 42-1 50 ° C. Example 2: Intentional Synthesis of Copolymerization with Propylene Glycol Derivatives (Modified NPG) as Co-monomer (13 () 0 / 〇)

Put terephthalic acid (69.0 kg, 415.0 mol) and ethylene glycol (30.0 kg '483.0 mol) into a 200 liter stainless steel reaction tank with only branch pipes, stirring devices and oxygen inlets Medium heating. The temperature was maintained at 190 ^ 230 ° C, and the esterification reaction was performed while purging with nitrogen at a flow rate of 30 耄 L / min while stirring. The resulting esterified product was a PET polymer 486493 V. Explanation of the invention (8) -BHET [bis (2-hydroxyxyethyl) terephthalate]. After the vinegarization reaction reached about 90% conversion, the propylene glycol derivative (compound 3) obtained in Example 1 of 54 moles was added as a comonomer, so that the molar ratio of compound B to terephthalic acid was 丨3.0%, at the same time add the polymerization catalyst antimony trioxide (2 4 · 2 g) and phosphorus triphenylene (5 · 9 g). ·

The temperature continued to rise to 230 ° C. After about half an hour of reaction, the pressure gradually decreased. Within half an hour, the degree of vacuum decreased from 76 0 torr to 20 torr, and the temperature increased from 230 ° C to 260. ° C, at this time, the temperature was increased to 270 ° C, and the pressure was reduced to 0.2 Torr. The polymerization reaction was performed for about two hours to obtain a copolyester (compound C). The reaction yield was 98.5%. The composition of the obtained copolymeric vinegar was analyzed spectrally as follows: 111 guan 1? (0? 3 (: 0 (^): 7.6-7.5 (terephthalic acid group), 4.3-4 · 1 (hydrogen ethyl group), 3.8 (0CH2, NPG), 3.6 (OCH2, ethylene glycol), (K7-0.5 (CH3, NPG) (ppm). The content of compound B in this copolyester can be represented by the content of NPG, calculated by IPNMR spectrum as 12.5 mole% The chemical formula of compound C is:

CHs 2 ~ C-CH2-〇 CH3 Jy (C)

The experimental results are shown in Table 1. Example 3: Synthesis of a copolyester using a propylene glycol derivative (modified NPG) as a co-monomer (13.0 / 00) The test procedure is the same as that in Example 2. To test repeatability. The experimental results are shown in Table 1.

Page 13 486493 V. Description of the invention (9) ----------- Example 4: Synthesis of copolyester using propylene glycol derivative (modified NPG) as prostitute ^ I 0%) Experimental procedure It is the same as in Example 2, but the amount of propylene glycol extension B) is changed so that compound B and terephthalic acid ^ (combined 0%. The experimental results are shown in Table 1. The ear ratio is 10. Comparative experiment 1: The experimental procedure for the copolyester with NPG as a co-monomer (13.0%) is the same as in Example 2 above, but with NPG (ie, unchanged NPG) instead of compound b (ie, modified NpG) ) 〇NpG plus two ^ so that the molar ratio of NPG and p-benzene: formic acid is 13 ()%. Shown in the experiment 1. Compared with car parent test 2 · Total NPG as a comonomer (130%) The synthetic experiment procedure of polyester is the same as the above Comparative Example 1. To test the repeatability. The experimental results are shown in Table 1. Comparative Experiment 3: Synthesis experiment of copolyester with NPG as co-monomer (10%) The steps are the same as the above-mentioned comparative experiment 1, but the amount of NpG added is changed so that the molar ratio of NPG and terephthalic acid is 10.0%. The experimental results are shown in Table 1.

Page 14 486493 V. Description of the invention (ίο) Table of the comonomer copolyester melting point NPG rational round addition amount (mol%) A NPG content in the copolymerization vibration (mol%) B NPG loss ratio (% ) (AB) / A (%) r Example 2 Compound B 210 13.0 12.5 3.8 Example 3 Compound B 209 13.0 12.5 3.8 r Example 4 Compound B 220 10.0 9.7 3.1 Comparative Experiment 1 NPG 218 13.0 8.3 36 Comparative Experiment 2 NPG 218 13.0 7.5 42 Comparative test 3 NPG 231 10.0 6.8 32 NPG content in Gongge Sg: calculated from the integrated area value in the HiNMR spectrum. From the results in Table 1, it can be seen that the propylene glycol derivative (Compound B) of the present invention is The monomer, a copolyester produced by a two-step synthesis method, has a much lower NPG loss ratio than those using NPG. Therefore, with the present invention, the difference between the content of NPG in the copolyester and the theoretical amount can be greatly improved. Although the present invention is disclosed in the preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can make changes and decorations without departing from the spirit and scope of the present invention. Therefore, the scope of the present invention The scope of the patent application attached later shall prevail. «

Page 15

Claims (1)

486493 Public file 89103341: > Sixth month of application for patent Fan Ye · Application scope of patent: 1. A propylene glycol derivative having the following chemical formula (IH〇 一 (CH2) p- (R1 I > -CH2 -C-CH2_〇-R2, goods O-(CH2) q-OH (I) wherein R1 and R2 may be the same or different, and are H, (H-C8 alkyl,-(CH2) s X, Where X is a group of optional F, Cl, Br, I, NO 3, s is an integer from 1 to 5; and P and q may be the same or different, and are integers from 2 to 8. 2 The propylene glycol derivatives described in item 1 of the scope of the patent application, wherein 1-1 and 1 ^ 2 are (: 1-08 alkyl groups) 3. The propylene glycol derivatives described in the scope of the patent application item 2, wherein R1 and R2 Both are methyl. 4. The propylene glycol derivative as described in item 3 of the patent application scope, wherein both p and q are 2. 5. A method for preparing a copolyester, comprising the following steps: (a) making the Monophthalic acid or its esters and the first alkyl diol are subjected to an esterification reaction at atmospheric pressure and a temperature of 180 ° C. to 25 ° C. to obtain a dicarboxylic acid dibasic group. bis (hydroxyalkyl) bez enedicarboxylate] oligomer; and (b) the oligomer and the propylene glycol derivative represented by the chemical formula (I) described in item 1 of the patent application range at a temperature of 250 ° C to 280 ° C , Pressure 2 to 486493 Case No. 89103341% Year / Amendment VI. Application scope of patent: Copolymerization was carried out under 0.1 t r r to obtain the copolyester. 6. The method according to item 5 of the scope of patent application, wherein the propylene glycol derivative represented by the chemical formula (I) is prepared by the following steps: a propylene glycol compound represented by the formula (II), Esterification reaction of osmic acid or its esters with a second alkyl diol: R1 (II) 1 H0-CH2 —C-CH2-10HI R2 where R1 and R2 may be the same or different, and Is H, n-C8 alkyl,-(CH2) 3 乂, where 1 is optional free 卩, (: Bu 81 ', 1, ^ 3, s is an integer from 1 to 5. 7. Such as The method described in item 6 of the scope of patent application, wherein R1 and R2 are C 1 -C 8 xyl. 8. The method described in item 5 or 6 of scope of patent application, wherein the first phthalic acid or Its esters may be the same as or different from the second phthalic acid or its esters, and are selected from terephthalic acid, isophthalic acid, phthalic acid, biphenyldicarboxylic acid, naphthalene ring dicarboxylic acid, and Among the group consisting of esters, the method as described in item 5 of the scope of patent application, wherein the first phthalic acid or its ester is terephthalic acid. 10 as in the scope of patent application The method according to item 6, wherein the second phthalic acid or an ester thereof is dimethyl terephthalate (DMT). 486493 Case No. 89103341 > Month Amendment VI. Scope of patent application 1 1. If the scope of patent application is 5th or 1st, the number of carbons of the first and second alkyl diols is between 2 and 8. 1 2. If the scope of the patent application is 5th or the first alkyl diol and the second alkyl diol 1 3. If the scope of the patent application is the fifth, the propyl titanium should be carried out in the presence of a monoester catalyst. , Tetrabutyl titanium, calcium acetate, vinegar. 14. The reaction as described in item 5 of the scope of the patent application is based on the addition of tetrapropyl titanium, tetrabutyl titanium, antimony trioxide, diamond acetate, and tin acetate in the presence of a polymerization catalyst. The reaction in item 5 of the scope of the patent application is to perform the method described in item 6 in the presence of an additive. The method alcohol described in item 6 may be the same or not. Glycol. The method described above, wherein the esterification catalyst is a zinc acid, and the acid acid is described in the method described above, wherein the polymerization catalyst is antimony, antimony acetate, or two groups. The method described, wherein the additive is in a selective group. Wherein the same, and the one in which the esterification reaction is composed of four, the copolymerization is selective alcohol group, the copolymerization is free trimethyl ether