TW212187B - A novel production method of fireproof polyester - Google Patents

Abstract

A novel production method of fireproof polyester, which comprises of using dicarboxylic acid or its derivatives, and glycol as main materials, and uses phosphonic co-monomer of the following formula as third material to impart flame retardancy, (see claim 1) in which R' is hydrogen or methyl, and Ar is a substituted or unsubstituted phenyl group; the addition of salts of co-monomer in the reaction system or/and dicarboxylic acid salts of the formula R(COO)2M, in which R is an aliphatic group of a carbon number 2 to 8 or an aromatic group of benzene or naphthalene, M is an alkaline or alkaline earth metal, as co-catalyst in esterification and polymerization; the addition of the third material and co-catalyst occurrs at the condition that the esterification percentage of the dicarboxylic acid or its derivatives exceeds 90% and continuing reducing pressure to 15 mm Hg to undergo molten polycondensation.

Description

A6 B6 ΟΛ ΟΛ Qhj 5. Description of the invention (1) A method for manufacturing flame-retardant polyesters, mainly using comonomer salts or / and dicarboxylic acid salts in the system as flame retardants to provide flame-retardant properties , Not only improve the reactivity of the comonomer, but also make the comonomer react to the main chain to form a copolyester, its reactivity is significantly increased, and the amount of by-products can be reduced, while giving the polyester flame retardancy and physical properties , And good washing resistance, can be used as flame retardant fiber, flame retardant fabric, flame retardant nonwoven fabric, flame retardant film (flame retardant adhesive) and flame retardant plastic (Plastic), etc. As humans pay more and more attention to the safety of life and property, successively amend the anti-combustion laws and regulations, plus the flame-retardant polyester fiber can be used in curtains, carpets, blankets, mattress cloth, etc., for public places that need to pay attention to anti-combustion effect Such as large dining rooms, hotels, KTV, movie theaters, etc. provide fire resistance; it is very helpful for general home safety such as the elderly, children's pajamas, and home appliances, and it shows the importance of flame-retardant polyester materials. The development of general flame-retardant polymers can be carried out in the following three ways: 1. Blending method of adding flame retardant (blending) method: adding flame retardant by blending method, the advantages of this method are easy to manufacture, and the disadvantages are additives and polymers The inherent compatibility problem is likely to cause migration of flame retardant during processing, which reduces the flame retardant effect, and if it is used in Lewis fabric, it has the problem of poor washing fastness. 2. Finishing treatment method: For fabrics, a layer of flame retardant can be applied after weaving into cloth. The advantage of this method is the convenience of processing and construction. The disadvantage is that only the surface of the fabric has a flame retardant effect, and the flame retardant effect As the number of washing increases, it decreases, which means that the washing fastness is poor. 3. Copolymerization method: It is mainly used to have a flame-proof effect. (Please read the precautions on the back before writing this page). Install _ order. This paper is printed by the R Industry and Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy. Applicable to CNS Standard A 4 specifications (210 X 297 mm) 81.9.20,000 212187 V. Description of the invention (2) Comonomers are reacted onto the polymer backbone by copolymerization. So that the flame-retardant monomer has a chemical bond with the polymer chain. It is not affected by processing. The flame retardant will not migrate out of the surface and affect the flame retardant effect. For fabrics and nonwovens, the washing strip has excellent fastness, permanent flame retardant effect, and excellent physical properties. Printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Development of the Ministry of Economic Affairs. The present invention utilizes a copolymerization method to develop flame-retardant polyester. In the past, the method of developing polyester by copolymerization method used gas-containing (C1), bromine-containing (Br), etc. as flame-retardant comonomers. The color of polyester deteriorates, and the flame-retardant monomer containing phosphorus is used as a comonomer. The phosphorus comonomers developed so far mainly include TOYOBO'S GH launched by Japan Toyobo, Travel 270 of Hester and the phenyl phosphonic acid (PPA) referred to as PPA. The development situation is shown in the table (1) Since TOYOBO'S GH and Hoechst travel 270 are inflammable, the single skeletons are controlled by Toyobo and Hesidai respectively, so it is not easy to obtain. The benzoic acid used in this case is not only easy to buy, but also has not been successfully reacted on the polyester main chain so far, see table (1), the inventor broke through that benzoic acid is not easy to be connected to the main bond and is easily evacuated and the loss is large Difficulties, using a new common media system, successfully made PPA highly reactive to the polyester main chain, so that the reaction rate of the comonomer is increased, that is to say, the phosphorus content in the copolyester is increased, and the flame retardant effect is improved , One can reduce the amount of phthalic acid and reduce production costs, and then can inhibit side reactions in the reaction, reduce the content of by-products in polyester, improve the heat resistance of the product, improve the color of polyester, and successfully develop New products, increase profits and increase product competitiveness. The difference between the present invention and the previous technology can be aimed at ⑴ flame retardant polyester synthesis process ② 81 * 9.20 * 000 (please read the precautions on the back before filling in this page) This paper scale is applicable to China ’s B Family Standard (CNS) A4 specifications (210 X 297mm) A6 B6 2j21R7 5. Description of the invention (3) (please read the notes on the back before filling in this page) The types of additives used and the advantages and disadvantages of the effects are compared, and the comparison is listed in the table (2 ). That is, the main purpose of the present invention is to provide a novel method for manufacturing a flame-retardant polyester, to solve the difficulty that phenylacid is not easily reacted to the polyester main chain and is easily evacuated by vacuum, so that phthalic acid can be esterified at a higher temperature Chemical reaction and increase the speed of decompression to carry out polycondensation reaction, and make phenylphosphonic acid react to the polyester main chain. One of the objects of the present invention is to provide a novel method for manufacturing flame-retardant polyester, the special emblem of which is to use flame retardant comonomer salts or / and salts of dicarboxylic acids in the system as co-catalysts It not only improves the reactivity of the co-monomer, but also reacts the comonomer to the main yam to form a copolyester, its reactivity is significantly increased, and the amount of by-products produced is reduced. It is a method that reduces costs, has simple steps, and is suitable for industrial production. Another object of the present invention is to provide a method for synthesizing a flame-retardant polyester. The flame-retardant polyester produced is provided with flame-retardant properties and physical properties, and has good wash resistance, excellent color, and is available for It is flame retardant fiber, flame retardant fabric, flame retardant nonwoven fabric, flame retardant film, flame retardant adhesive and flame retardant plastic. Printed by the Central Standard of the Ministry of Economic Affairs, β-Consumer Cooperative Co., Ltd. to produce a flame-retardant polyester mainly composed of monomers of dicarboxylic acids and glycols, using polyprotonic acid that provides flame-retardant comonomer The polyprotonate of dicarboxylic acid in the salt or system is a co-catalyst, the concentration of which is 0.05 ~ 1 times of the flame retardant comonomer, and preferably the ester is in the presence of 0.02 ~ 0.40 times of mole. Chemical reaction, and then the polycondensation reaction is carried out at higher temperature and under reduced pressure. The term "flame-retardant polyester composed mainly of units of dicarboxylic acids, polyols and benzoic acid" here refers to dicarboxylic acids and their derivatives. This paper is also applicable to China National Standards (CNS) A 4 Specifications (210 X 297 mm) 81.9.20,000 Printed by the Ministry of Economy, Central Standards Bureau, S Industry and Consumer Cooperatives «212187 A6 __________ B6 V. Description of the invention (4) (Diesters of dicarboxylic acids) and polyols Polyesters and any co-condensable polyacids and esters of polyacids, copolyesters made from polyols. Among them, dicarboxylic acids, diols, polyacids, esters of polyacids and polyhydric alcohols, the representative compounds are terephthalic acid (Terephthalic acid), isophthalic acid (isophthalic acid), adipic acid (Adipic acid), sebacic acid, azelaic acid, dodecane dicarboxylic acid, hexahydroterephthalic acid, terephthalic acid Methyl vinegar, dimethyl isophthalate, 5-sulfonic acid dimethyl isophthalate sodium salt SIPM (sodium salt of Dimethyl, 5-su 1 foisophtha1 ate), 5-sulfoisophthalic acid sodium ethyl salt (bis (2-hydroxyethyl) 5-sulfoisophthalate sodium salt) and 2,6-naphthalene dicarboxylic acid (2,6.-naphthalene dicarboxylic acid) and their diacetates and ethylene glycol, 2,2-di Methyl propylene glycol (neopentyl glycol), 1,6-hexanediol (1,6-hexanediol), 1,4-cyclohexane dimethanol (1,4-cyclohexanedifflethanediol), Polyethylene glycol (Polyethylene ether glycol), Polybutylene_diol (Polytetr * -amethylene ether glycol), etc., dibasic acid and glycol can be used separately Use or combine several uses. 0

II The flame retardant comonomer used in the present invention has the formula Ar_P— (〇R) 2 R is (CHz) η Η, η is from 0 to 3, Ar is substituted or unsubstituted is usually phenyl (phenyl "Base" "naphthyl, alkoxy, aralkyl, etc. 6 This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 81 · 9 · 20 · 000, (please read the precautions on the back before writing this page) i. Order. 2 Qing 7

AB Central Ministry of Economics- " -Bureau R Industry and Consumer Cooperatives Printed 5. Description of Invention (r) The present invention uses polyprotonates as co-catalysts. The polyprotonates used to provide flame retardant co-money The salts of the body, or the salts of dicarboxylic acids, or the salts containing more than two protons, may be sodium phenylphosphonate, potassium phthalate, ammonium phthalate, etc. or the general formula is R (COO) 2 Μ Dicarboxylic acid salt, where R is a saturated aliphatic group of 2 to 8 carbon atoms or aromatic group of benzene and tea, and M is an alkali gold or alkaline earth metal, represented by potassium terephthalate (potassium tere- phthalate), 2,6 — naphthalene dicarboxylate, sodium adipate, sodium oxalate, sodium suc.cinate, p-benzene Formic acid fit (magnesium terephthalate), these organic acid salts can be used alone or in combination. The amount of these compounds added is 0.5 mol% to 100 mol%, preferably 2 mol, relative to the ortho-acid co-monomer Ear% to 40 mol%. The surprising effect is that in addition to significantly improving the reaction of the phosphonic acid co-plow body to the main chain, it can also reduce the by-products produced in the synthesis of polyester, such as diethylene slycol when synthesizing flame-retardant PET The content in polyester and the amount of tetrahydrofuran produced during synthesis of flame retardant PBT, etc. It is beneficial to improve the properties of flame retardant polyester such as physical properties, color and melting point. The synthesis of the flame-retardant polyfill described in the present invention has a molar ratio of diol to dicarboxyl (or dicarboxylic acid ester) of 1.1: 1. 〇 to 2. 〇:]. 〇S 好 足 1 15: 1. 〇 to 1.8: 1.0, the esterification temperature takes 1 851: to 270_e ίΰ good enough to 2501, when the esterification conversion rate is 90% to :: S good enough 95% to 丨.:, The addition of phthalic acid strips will ignite the public, and the co-catalyst can be added here. The paper esters are suitable for the Chinese National Standards (CNS) Jiaku (2ι〇Χ297mm) (please first Read the precautions on the back and then fill in this page). Install _ Ministry of Economic Affairs Central Standards Employee Elimination # Cooperative Society «212187 Α6 _ Β6 V. Description of the invention (6) Add it at the time of conversion, wait for the esterification rate of the flame retardant comonomer Between 80% and 99%, preferably between 85% and 95%, starting from 245C to 285Ό and the general polycondensation method is known as antimony trioxide as a catalyst, the pressure is less than 1.5mniHg for polycondensation reaction. The synthetic flame-retardant polyester obtained by the present invention has a high phosphorus content in the main bond of the polyester, and is used for fibers, films and plastics with good properties, good flame retardancy and high utilization value. Regarding the present invention, the technical means and functions adopted are described later. It is believed that the purpose, characteristics and advantages of the manufacturing method of the present invention can be obtained from an in-depth and specific understanding, these embodiments are only essential descriptions, However, the content of the present invention is not limited to the cited embodiments. Example 1 Put 119.δ9 g of diethyl terephthalate (BHET), 166 g of terephthalic acid (TPA) and 102.61 g of ethylene glycol (EG) into a fractionation tube, stirring device and nitrogen The reaction mixture was heated in the 1.5-liter stainless pin reaction tank at the inlet and the temperature was maintained at 190 ~ 230t, while being stirred while being flushed with nitrogen at a flow rate of 30ml / min, the esterification reaction proceeded to a conversion rate of more than 90%, and then added 15.177 Grams of flame retardant comonomer phenylphosphonic acid (PPA) is 8 mol% relative to TPA, co-catalyst 4.δ 5 g sodium phenate (Na2PP) dissolved (relative to PPA 20 mol%), 14.88 g EG and 0.0S75 grams of three gasified diantimony maintain the original esterification temperature in the reaction system and continue the esterification reaction of PPA. After the conversion rate of PPA esterification reaches 85%, the mixture produced by the above esterification reaction continues to raise the temperature to 260t: And gradually reduce the pressure within 40 minutes, and this paper scale is applicable to the Chinese Standard (CNS) A 4 specification (210 X 297 81.9.20,000 X, please read 4? Precautions on the back before writing this page) 丨. Order. A6 B6 212187 V. Description of the invention (7)

Maintain vacuum pressure less than ImmHg for 2 hours to produce flame retardant polyester, DEG content 2.46%, melting point 243.61C, limiting viscosity 0.65, acid value 17.1, L value color is 71.3, analysis and identification reaction to the PPA reaction rate on the main bond of the polyester It was 89.1%. The silk after spinning at 2651C was reanalyzed by " P-NMR. The reactivity of the PPA in the primary bond remained the same as before spinning without loss due to the spinning process. Embodiments 2 to 6: The method according to Embodiment 1, wherein the amount of the co-catalyst sodium phenoxylate relative to PPA is changed to 2 mol%, 4 mol%, 10 mol% and 40 mol% respectively. Other reaction conditions Similarly, the properties of the synthetic flame retardant polyester are listed in Table (3). Embodiments 7 to 8 according to the method of embodiment 1, in which the co-catalysts were changed to potassium terephthalate (OU TP), sodium adipic acid (Naz AA); the other reaction conditions are the same, the synthesis of the flame-retardant polyester The properties are listed in Table (3). Embodiments 9 to 12: The method according to Embodiment 1 in which the addition amount of the flame-retardant comonomer PPA is changed to 5%, 12%, 15% and 20% relative to TPA As with other reaction examples, the properties of the synthesized flame-retardant polyester are listed in Table (3). Example XIII. This paper size is applicable to the National Standard (CNS) A4 specification (210 X 297, dream) (Please read the precautions on the back before writing this page) 81.9.20,000 A6 B6 212187 printed by the Bureau of Standards, Industry and Consumers Co., Ltd. V. Description of the invention (8) Combine 166 grams (1 mole) of terephthalic acid with 153 grams (1.5 moles) of 1.4 butanediol, 0.2 TPA weight % Tetrabutyl titanate (tetra butyl Utanate) and a total of 3.23 grams of Na2 PP (relative to 20mole% of the PPA added in the second stage) were placed in the reaction tank in Example 1, the reaction mixture was heated, and the temperature was maintained While stirring at 200-2101C, nitrogen gas with a flow rate of 25 ml / inin was flushed. After 80 minutes of reaction, 46.6 g of water was distilled, which contained 9.28 g of THF. The conversion rate at this time was 95.2%, and then 10.118 g of PPA was added relative to TPA 8iaole%; When the esterification rate of PPA reaches 90%, the mixture produced by the above esterification reaction will continue to raise the temperature to 260¾ and gradually reduce the pressure within 40 minutes and maintain the vacuum. And maintain a vacuum of less than 1.5raittHg for 105 minutes to prepare a flame-retardant polyester with an ultimate viscosity of 1.15, an acid value of 14.5, a melting point of 2181C, and UeiP-NMR analysis to identify the PPA reaction rate from the main polyester to 93.1%. Example 14 The method of Example 13 was used, in which the TPA terephthalate was changed to DMT terephthalate, the amount of tetrabutyl titanate catalyst was changed to 0.1%, and the other reaction conditions were the same The PPA reaction rate of the synthesized flame-retardant polyester is 94.3. Other properties are listed in Table 4. Example 15: 166 grams (1 mole) of TPA, 43.8 grams (0.3 moles) of adipic acid AA 135 grams (1.5 moles) of 1,4-butanediol, TPA, and AA by weight of 0.2 ± tetrabutyl Based on titanate and 3.32 g (20 mole) Na2 PP, according to Example 10 The paper size is applicable to the National Standard (CNS) A 4 specifications (210 X 297 public goods) (please read the precautions on the back side first Write this page) i Pack-Book · Printed by the Central Standards Bureau of the Ministry of Economic Affairs, 8 Industrial and Consumer Cooperatives 81.9.20,000 212187 V. Description of the invention (9) 13 Conditions 53.53 grams of water are distilled out after 79 minutes of esterification reaction, which contains 9.95 grams of THF, the conversion rate at this time is 89.6%, the PPA reaction rate of the synthesized flame-retardant polyester is 93.7%. (Please read the precautions on the back before writing this page) -'β

I The scale of papers printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 81.9.20,000 212187 a6 _ _ ._B6_ V. Description of invention (10), (please (Read the notes on the back first and then write this page) Comparative Example 1 is the same as the method in Example 1, in which the co-catalyst is changed without adding other reaction conditions, and the properties of the synthesized flame-retardant polyester are listed in Table 2 ). Comparative Example 2. According to the method of Example 1, wherein the total Na 2 PP is added to 1.2 g of NaOH, the other reaction conditions are the same, and the properties of the synthesized flame-retardant polyester are listed in Table (3). * · Comparative Example 3 According to the method of Example 13, in which the co-catalyst is changed without adding other reaction conditions, the properties of the synthesized flame-retardant polyester are listed in Table (4). Comparative Example 4 According to the method of Example 15, in which the cocatalyst was not added, the other reaction conditions were the same, and the properties of the synthesized flame-retardant polyester are listed in Table (4). Printed by the Employee Consumers of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs #Cooperative

2 1X This paper is also applicable to the Chinese and Western Standards (CNS) A 4 specifications (210 X 297 mm) 81.9.20,000 212187 A6 B6 5. Description of the invention (11) 11 ^ 60-1856: PPAm 钭 ΗΜΛ.Λ / USP 3,941,752 window jUSP si ^ 936 (1977j Hoechst iiNi ¾2

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Sbz 〇3, 280rf g-APPA si ψ3π >-> FR 3 TPA + EG cop): ψ < Itorr IV = 0.52 conveso-n 96% DKr + EG-> Β1ΠΓΓ Ivno.22 3 1 1ΙΦ->->-> if. .In-丨 installed. 0 Although 7iB + order. Sl ± lsllhr 3ilJ -h I— 0 0 ^ § printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 81.9.20,000 21218 ^ A6 B6 V. Description of invention (μ)%

isJ (please read the notes on the back before writing this page) 輺 沛 Flsl dysprosium palace Η 蚶 砘 谇 唞, ΒΙΛΙΗ 蒒 蓊 胗 "Shu Zeng 钒 钭 Ling marriage-Μ 鞅 (涞 埘 洚 沛 鼸 delete 卅馘) _ $ 涊 13.7 times chaos 0 knots to delete the tan array, Sun Palace :! Europium porphyra _ 00 繇 繇 翔 0 > Pug Ukrainian M class title Xue M 0 0 'Pack. ^^ Wei = Tibet ^^ Jin 5 ^ Miscellaneous ^ = st 痩 麻 1— 钭 賧 涅 萍 潷Order · Printed by the KK Industrial and Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ♦ Indication _ 薤 、 > reward_ "Sui 眇» II 幑 从 Pei Xian Shu Jue Pei Mi Η + 宅 ± 〇〇0 次 ±± ♦铿 啦 钭 • Yunai rubidium This paper standard is applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) 81.9.20,000 A6 B6 Printed by Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs I5) wm \ mm single PPA content mm force 0MISIS class Tm (° C) m. L degree secondary surface DEGCi;) IV (g / dl) mm (raeq / kg) PPA bh (96) Broach __. 8 20% NazPP 243.6 71.3 2.46 0.655 17.1 89.1 (Broad) II 8 2% NazPP 237.5 72.7 '4.18 0.671 * 15.2 32.6 (Broad) Τ3Γ 8 A% NaaPP 238.1 70.2 4.06 0.613 11.4 29.2 (Broad) IV 8 6% NazPP 244.1 73.2 1.96 0.647 14.4 74.0 (Broad) 5 8 10¾ Na ^ PP 241.1 68.5 2.84 0.761 11.3 75 7 (Br ^ ad) _L- 8 Na Ha ^ PP 246.6 74.2 2.45 0.545 17.1 78.7 (Broad) Seven 8 20% KzTP 244.2 71.8 2.61 0.621 16.3 86.7 (Broad) 8 8 20% NazM 243.5 71.5 2.72 0.633 15.8 85.8 (Broad) 9 5 20% Ha2 PP 243 72.8 2.24 0.643 15.4 88.7 (Broad) 10 12 20% NaiPP 238.4 71.4 2.64 0.655 17.2 90.6 (Broad) 11 15 2m Na2 PP 233 70.6 2.76 0.714 13.7 qi 7 (Briad) 12 20 20¾ NazPP 228 69.5 2.93 0.662 17.8 90.4 (Broad) 8 0% 235 65.5 5.31 0.593 17.0 9.6 (Sharp) 8 20% NaOH 228.8 68.9 5.67 0.695 15.8 14.3 ( (Sharp) Tables (3) Actual remuneration from 1 to 12 and _ Example 1 of 17-Please read the precautions on the back before writing this page) This paper scale is applicable to China Yuanjia Standard (CNS) A 4 specifications (210 X 297 Mm) 81.9.20,000 212187 Printed by the Ministry of Economic Affairs, Central Standard, MC Industrial and Consumer Cooperatives V. Description of the invention (16) Examples of comonomer content Co-monomer content Co-catalyst types and content Tm (° C) Chromaticity L Degree by-product THF Decrease IV value The percentage of PPA reaction to the main chain (%) (aiP-HMR peak shape) 13 8 8% Naa PP 218.1 71.2 3.7 I.l5 93.1 (Broad) 14 8 20% Na2 PP 217.3 71.8 1.2 1.09 94.3 (Broad) 15 15 20% Ha2 PP 174.6 70.7 5.6 l.2l 93.7 (Broad) Comparative Example 3 8 0 214.2 70.4 0 I.l8 13.5 (Sharp) Comparative Example 4_ 8 0 172.4 68.6 0 1.24 15.6 (Sharp) Table (4) Synthesis of Examples 13 to 15 and Comparative Example 2 Properties of flame retardant polyester

8 1X (Please read the precautions on the back before writing this page). Packing. Ordering. 1 The paper size is applicable to China National Standard (CNS) Grade 4 (210 X 297 mm) 81.9.20,00

Claims (1)

6. Scope of patent application Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 1 · A method for manufacturing flame-retardant copolyesters, using pseudocarboxylic acid or its derivatives, and glycol as the main raw materials, providing flame-retardant properties Phosphorus comonomer 0 Ar — P — (OR ') 2 is the third component raw material, where R' is a hydrogen atom or a methyl group, and Ar is a substituted or unsubstituted phenyl group; Monomer salts or / and dicarboxylates with the general formula R (C00) 2 Bu |, where R is an aliphatic group of 2 to 8 mega atoms or an aromatic group of benzene and Cai, M is a Alkali metal or alkaline earth metal is a co-catalyst for esterification and polymerization; the above-mentioned third component and co-catalyst are added to the dicarboxylic acid or its derivative with an esterification rate of 90% or more, and the pressure is reduced to 15nnnHg Melt polycondensation to make flame retardant copolyester. 2. The preparation method as described in item 1 of the patent application scope, wherein the co-condensable dicarboxylic acid or its esters and diols are commonly used compounds, including isophthalic acid and adipic acid ( adipic acid) Sebacicacid, aze 1 aicacid, dodecane (Hcarboxylic acid), hexahydrote "ephtha Π cacid", 5-cat SI PH (sodium salt of Dimethyl, 5 _ su 1 f ο ί sophtha 1 atc;), 5-¢ 3 acid question diethyl fill sodium salt S IP l ·: (b Ls (2-hydroxyethy)) 5-sulfoisophthalate sodium salt,) and 2,6-tea dicarboxylic acid (2,6-naphl: ha 1 enedicarboxy 1 ic acid) and its diesters; and ethylene glycol Uthylerue glycol), 2 , 2 —Dimethylmalonate (neopenty 1 g 1 yc ο 1), 1, β — l! Second leaven (please read the precautions on the back before filling in this page) • Pack. Order _ This paper size is for China National Standard (CNS) A 4 specifications (210 X 297 public exchange) 81.9.10,000 21 2167 A7 B7 C7 D7 VI. Patent application range (l, 6-hexanediol), 1,4-cyclohex anedimethanediol (Polyethylene ether glycol), polybutylene Polytetramethylene ether! Glycol, etc., dicarboxylic acids and diols can be used alone or in combination. 3. As described in item 1 of the patent application, the co-catalyst means to provide flame retardant Characteristic comonomer salts or dicarboxylic acid salts or salts containing more than two protons, can be sodium phosphonate, potassium oxalate, ammonium oxalate ', sodium phosphate, potassium phosphate, or the general formula is R ( C00) 2 M dicarboxylic acid salt, wherein R is an aliphatic group of 2 to 8 carbon atoms or an aromatic group of benzene and naphthalene, M is an alkali metal or alkaline earth metal; these salts can be used alone or in combination , The dosage is 0.5 mol% to 100 mol% of the phosphorus strip comonomer, preferably 2 mol% to 40 mol% 4. The method as described in item 1 of the patent application scope, in which melt polycondensation is legal When the esterification rate (or transesterification rate) of dicarboxylic acid or dicarboxylic acid ester and diol is more than 90%, add phosphorus bar The co-catalyst can be added at this time or added in the previous stage. The esterification rate of the co-monomer is between 80% and 98%, preferably between 85% and 95%, at 245 ° C It is best to reach 285 ° C, 250Ό to 270 ° C, and start polycondensation and anti-nicking under the pressure of less than 1.5mmlls. 5. The method as described in item 1 of the range of the Chinese variegated range, in which the general formula of the phosphorus comonomer is 0 Λ "-P- (0R ') 2, R' is a hydrogen atom or a Φ group, Ar is 苻; change Or _ 1 —— T --- 1 I (please read the precautions on the back before filling in this page) • Install. -ΤΓ. This paper is printed by the Central Legal Bureau of the Ministry of Economic Affairs of China. This paper standard is applicable to China ’s national standards (CNS) A4 specifications (2) 0 X 297 conversion) 81 · 9 · * ϊ ^ 〇212187 Α7 Β7 C7 D7 VI. Patent application scope to replace phenyl, this phosphoric acid comonomer is added in the amount Relative to the phosphorus content in the copolymerized vinegar is 0.2-12%. 6. The method as described in item 4 of the patent application, wherein the molar ratio of glycol to dicarboxylic acid (molar ratio) is 1.1: 1.0 to 2.0: 1.0, the most Fortunately, it is between 1.15: 1.0 and 1.8: 1.0. 7 As described in item 4 of the patent application, the esterification reaction is carried out at 160 to 280 ° C, and preferably at 190 to 260 ° C. ( Please read the note on the back 'Issues before filling out this page)-Binding-Order. The Central Standards Bureau of the Ministry of Economic Affairs, S Industry and Consumer Cooperation Du printed this paper standard is applicable to China National Standards (CNS) A 4 specifications (2 丨 0 X 297 male seam