300903 A7 ---B7__ 五、發明説明（1) 本發明係有關於磷条不飽和聚酯之製法，待別是有两 於一種利用有效金屬_媒與有機酸之组合降低反應溫度， 能以一次加料反應方式將磷單髏反應至共聚酯鏈上。 根據既有難燃不飽和聚酯技術，主要可分為添加型及 反應型二種型式，添加型僳以氫氣化鋁，鹵素合併三氣化 二銻、或磷/鹵化合物等難燃爾直接添加至不飽和聚酯而 得，其優點是使用方便，價格便宜，但已知其缺點為添加 董需很大，才能達到難燃效果（50%以上），且會彩«材 質物性，並會造成難燃劑遷移至表面的問題，而由於難燃 劑之避移性，日久亦會降低難燃待性。除此之外，無機難 燃爾添加量增多，亦會發生樹脂黏度上升，而迪成加工困 難的問題。 反應型不飽和聚酯傜以鹵素或磷/鹵化合物直接反應 至共聚酯鐽上，所得產品可克服添加型之物性低下及加工 問題，並且難燃劑不會邏移至材質表面，可長久保持難燃 特性，但其缺酤是價格昂贵，不易普及。 經濟部中央標隼局員工消费合作社印製 (請先閱讀背面之注意事項再填寫本頁) 不論是添加型或反應型不飽和聚酯，若使用含鹵素之 難燃劑，則燃燒時會產生含鹵有毒氣體並迪成濃煙，反而 對逃生不利。近年來因應公共安全及琛保需求，已朝向無 鹵低煙化發展。目前難燃不飽和聚酯以鹵素或無機型為主 ，在磷条方面卻少有進展，現今既有技術美國專利366202 5 ,是以篇化合物反應至聚酯鰱上合成反應型磷条不飽和聚 酯，此技術所採用的方式是以二元酸/酸酐輿過量的二元 酵反應先行合成一種終螭具有氫氣基的共聚膽，第二步蹶 -3 - 本紙張尺度適用中國國家標準（CNS > A4規格（210X 297公釐） 經濟部中央標準局貝工消費合作社印裝 A7 B7 i、發明説明（2 ) 是磷酸酯舆有機質子酸或内酯反慝，形成一種含有磷酸酯 之中間體，第三步雄則将已合成之終端具有氫《基的共聚 酯及含磷酸酯之中間體一起反應成為含磷之不飽和聚酯， 整腰反醮不僅箱要三鹤步《，且分別霈以不同批次進行反 應，對於廠化量產而言，需要多重的批次設锵，以及繁多 的步«，若以資源、人力、時間而言，均不合乎經濟效益 Ο 有鑑於前述習知技術之缺黏，本發明之目的乃是要提 供一種磷条難燃不飽和聚酯，不僅不含鹵化物，且可克服 添加型所造成物性降低，邏移性及加工性之問題，並提供 一種製法可降低反應溫度，以一次加料的反窸方式合成產 品，簡化既有技術痛要三批次及三值反應步《的程序，並 且不需增添反應設備，直接使用一般不飽和聚酯之原設備 即可生產產品。 為了逹成本發明之上述目的，本發明之製法藉由反應 條件設計，利用有效金羼觸媒舆有機酸之姐合，降低反應 ..„.............. ........... ....... ifi度，使能以一次加料反應方式將磷單體反應至共聚酯鰱 上。除此之外，經由導m鱼物之莫耳數，能有效控制 磷含量。合成之寡聚物再摻配含雙鍵之反應性單龌，形成 具有難燃防火性質之不飽和聚酯。 本發明所製得之磷条難燃不飽和聚酯符合一般不飽和 聚酯待性，能利用不同加工方式製成各種不同塑謬製品， 應用於強化塑_方面的有公共建材、交通蓮輸及家«產岛 等，除此之外，也可應用於SNC、BMC，睡殼等方面，應用 -4 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 11— I —裝 I 11 ^ ^ ί'^ f·. · - · 4 * - (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 3〇〇9〇3 A7 _B7_ 五、發明説明（3 ) 市塲廣大。 本發明之製作方法詳逑如下： 反應檐中導入氮氣流，然後一次加入磷化合物，飽和 二元酸或二酸酐含雙鍵之二元酸或二酸酐、觸媒、安定劑 ，反鼴粗度控制在140-1901之下進行共聚合反應，而以 150-180TC最佳；分皤粗度控制在90-105*C ;反應遇程中 觀察酸價及皤出率的變化，反應至8-10小時酸價逹70-90 s. KOH/g ,且不再有明顯變化後，抽低真空1 -3小時 (10-20 torr),而後可得磷糸難燃不飽和聚酯。 以上所得之磷条不飽和聚酯需以反應性單體（内含抑 制劑）稀釋，並加入促進劑後才能進行下一步的加工硬化 處理。 依照本發明之製法所採用之磷化合物结構為： 0 II/0R2300903 A7 --- B7__ V. Description of the invention (1) The present invention relates to the preparation method of phosphorus-saturated unsaturated polyesters, except that there are two or more of which use a combination of an effective metal-intermediate and an organic acid to reduce the reaction temperature. One-time feeding reaction method reacts the phosphorus single skeleton onto the copolyester chain. According to the existing flame retardant unsaturated polyester technology, it can be divided into two types: additive type and reactive type. The additive type is aluminum hydride, halogen combined with three gasified antimony, or phosphorus / halogen compound and other flame retardant direct addition. It is derived from unsaturated polyester. Its advantages are easy to use and cheap, but its shortcomings are that the addition of Dong needs a large amount to achieve the flame retardant effect (more than 50%), and it will color «material properties and will cause The problem that the flame retardant migrates to the surface, and due to the repellency of the flame retardant, it will also reduce the flame retardancy over time. In addition, if the amount of inorganic flame retardant added increases, the viscosity of the resin will increase, which will cause difficulty in processing. The reactive unsaturated polyester is directly reacted on the copolyester with halogen or phosphorus / halogen compounds. The resulting product can overcome the physical properties and processing problems of the additive type, and the flame retardant will not move to the surface of the material for a long time. Maintain the flame-retardant characteristics, but its shortcoming is that it is expensive and not easy to popularize. Printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) Whether it is an additive or reactive unsaturated polyester, if a halogen-containing flame retardant is used, it will be generated when burning The halogen-containing toxic gas is combined with dense smoke, which is not good for escape. In recent years, in response to the needs of public safety and security, it has developed towards halogen-free and low-smoke. At present, the flame-retardant unsaturated polyester is mainly halogen or inorganic type, but little progress has been made in the phosphorus strip. The existing technology US patent 36620 25 is based on the reaction of the compound to the polyester silver carp. Polyester, the method used in this technology is to first synthesize a bile acid / anhydride and excess binary enzyme reaction with a hydrogen peroxide-based copolymer bile, the second step is -3-This paper scale is applicable to Chinese national standards ( CNS > A4 specification (210X 297 mm) A7 B7 printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs i. Description of invention (2) It is a phosphate ester and organic protonic acid or lactone, which forms a phosphoric acid ester. Intermediate, the third step is to synthesize the co-polyester with hydrogen terminal at the terminal and the phosphoric acid ester-containing intermediate together to form phosphorus-containing unsaturated polyester. , And each batch reacts in different batches. For factory mass production, multiple batch installations are required, as well as many steps «, in terms of resources, manpower, and time, it is not economically beneficial. Given the aforementioned knowledge The purpose of the present invention is to provide a phosphorous flame-retardant unsaturated polyester, which not only does not contain halides, but also can overcome the problems of reduced physical properties, logic migration and processability caused by the additive type, and provides A preparation method can reduce the reaction temperature, synthesize the product by the reverse feeding method of one-time feeding, simplify the procedures of the existing technically demanding three batches and three-value reaction steps, and directly use the general unsaturated polyester without adding reaction equipment. The original equipment can be used to produce products. In order to achieve the above purpose of the invention, the method of the present invention is designed by the reaction conditions, using the effective combination of Jin Jin catalyst and organic acid to reduce the reaction ......... ............................... ifi degree, which can react phosphorus monomer to copolyester silver carp in one feeding reaction. In addition, the phosphorus content can be effectively controlled by the number of moles of the fish. The synthesized oligomer is blended with a reactive monochelic containing double bonds to form an unsaturated polyester with flame retardant and fireproof properties. The phosphorous flame-retardant unsaturated polyester prepared meets the requirements of general unsaturated polyester and can be used Processing methods make various plastic products, which are used in strengthening plastics. They include public building materials, transportation lotus and home islands. In addition, they can also be used in SNC, BMC, sleeping shells, etc. -4-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 11— I — Install I 11 ^ ^ ί '^ f ·. ·-· 4 *-(Please read the precautions on the back first (Fill in this page) Printed 3,009,003 A7 _B7_ by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (3) The market is vast. The production method of the present invention is detailed as follows: Introduce nitrogen flow into the reaction eaves, and then Add phosphorus compound at one time, saturated dibasic acid or dianhydride containing double bond of dibasic acid or dianhydride, catalyst, stabilizer, co-polymerization reaction under the control of 140-1901, and 150-180TC The best; the thickness of the sub-grain is controlled at 90-105 * C; the changes of acid value and output rate are observed during the course of the reaction. The acid value is 70-90 s. KOH / g after 8-10 hours, and no longer After there is obvious change, draw a vacuum for 1-3 hours (10-20 torr), and then obtain the phosphorous refractory unsaturated polyester. The phosphor-saturated unsaturated polyester obtained above needs to be diluted with reactive monomers (containing inhibitors) and added with an accelerator before the next work hardening treatment. The structure of the phosphorus compound used in the preparation method of the present invention is: 0 II / 0R2
Ri - < (Ri,IU,R3為氫，烷芳基，苯基，烷基， \〇Ra 芳烷基，其中烷基具有1-4傾硪）琪例而言，如苯除酸 (phenyl phosphonic acid)，甲基路酸二甲酯 (dimethyl _ethyl phosphorotate)，乙院除酸二乙酯 (d i e t h Jr 1 e t h a n e p h 〇 s p h ο n a t e) » 甲院 R 酸二乙®Ri-< (Ri, IU, R3 is hydrogen, alkaryl, phenyl, alkyl, \ 〇Ra aralkyl, wherein the alkyl group has 1-4 inclination) For example, such as benzoic acid ( phenyl phosphonic acid), dimethyl _ethyl phosphorotate, dieth Jr 1 ethaneph 〇sph ο nate »甲 院 R 酸二 乙 ®
(diethyl aethane phosphonate) > 乙院除酸二甲酯 (diaethyl ethane phosphonate) » 丁院除酸二丙 ffi (di p r o p y 1 b u t a n e p h o s p h ο n a t e〉，苯膦酸二異丁酯 (d i i s o b u t y 1 b e n z e n e p h o s p h ο n a t e)，苯转酸二苯 IB (diphenyl benzene phosphonate)等碟酸 _ 類化合物。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） --------{—裝------訂--Ί—^--«---{冰 *»-*- _ (請先閱讀背面之注意事項再填寫本頁) / / 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（4 ) 本發明所使用之二元酸、二酸酐及二元酵是一般不飽 和聚酯常用之化合物，其中飽和二元酸為原苯二酸 (〇 r t h 〇 p h t h a 1 ί c a c i d)，苯二酸 gf (p h t h a 1 i c a n h y d r i d e) ，異苯二酸（isophthalic acid)，以及四氫苯二酸 (tetrahydro phthalic acid)，六氫苯二酸 (hexahydrophtha 1 i c acid) » 四氣苯二.酸（tetra chlorophthalic acid)，己二酸（adipic acid),二聚亞麻 子油（diierized linseed oil)及大豆油脂肪酸（soy bean o i 1 f a 11 y a c i d)及酸ffF (a n h y d r i d e)等；含雙鍵之不飽 和二元酸為馬來酸（aaleic acid)，馬來辭（naleic anhydride)，寓馬酸（fuaaric acid)，衣羼酸（itaconic acid)摔中屬酸，（citraconic acid)，中康酸（aesaconic acid)，阿康酸（aconic acid)等；二元酵為乙二酵 (ethylene glycol)，丙二酵（propylene glycol)，二甲 基乙二酵（dimethyl glycol)，二丙嫌乙二酵（dipropylene glycol), 1— 4 丁烷二酵（1-4 butanediol),新戊基乙二 酵（neopentyl glycol)，戊基乙二醇 （pentyl glycol) ，氣化院基雙齡（oxyalkylated bisphenol)，氫化雙勘 (hjrdrogened bisphenols)等·· 二元酸和二元酵可單獨或 合併數種使用。 本發明製法中之_化反應所需二元酵對二元酸的比率 為1.03 : 1.0至3.0 : 1.0 ,飽和二元酸對含雙鍵二元 酸之比率為0.05 : 0.95至0.95 : 0.05 ; 磷化合物對飽 和二元酸之比率為0.05 ·· 0.95至0.95 : 0.05 , 其中磷 -6 - 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨OX297公釐） fvl ^in 1L ^^—^1 ^^1 J 洚 - : - (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 A7 ___B7_ 五、發明説明（5 ) 化合物莫耳數由0.1至0.7製成箱条不飽和聚酯之磷含量 為 0.1 至 10%。 本發明於反應過程中所使用之有效觸媒组合為金颺觸 媒合併有機酸，其中有機金腯觸媒如有機錫金靥氣化物類 ，舉例而言，如二丁基錫氣化物（dibutyl tin oxide)， 二丁基篇乙酸酷（dibutyl tin acetate)，氛化錫（Tin chloride)，草酸錫（Tin oxalate)，三氣化二錄（antimony oxide)，氣化转（Zinc oxide)，氣化好（calciu· oxide) 等，用置為0.01-0.(相對全部二元酸用曇），而最 適用量範圍為0. 1-0.5% ;有機酸如對甲苯磺酸（p-toulene s u 1 f ο n i c a c i d)、硫酸（s u 1 f ο n i c a c i d)、鹽酸（h y d「〇 g e η chloride)、袋酸（phosphoric acid)、三氯化联（phosphorus chloride)等，用*為0.01 - 0.6 wt% ,最適用量為 0.05-0.4¾ 〇 為嫌持反應遇程中之熱安定性，加入如受阻酚（hinder Phenol)類熱安定贿，用董為二元酸之0.01-0.5 vft %。 本發明製得之磷条不飽和聚酯最後以反應性單匾稀轉 ，此反應性單匾為含有乙烯（vinyl)官能基者如苯乙烯 (styrene)，甲基丙嫌酸甲® (methyl methacrylate)，乙 嫌基甲苯（vinyl toluene)，二乙嫌基苯（divinyl benzene )，丙嫌酸甲酷 （methyl acrylate)，丙嫌酸乙(ethyl acrylate)，甲基丙烯酸乙 _ (ethyl eethacrylate)，甲 基丙烯酸異丁酯（n-butyl nethacrylate)，甲基丙烯酸 正丁酯（n-butyl lethacrylate)，丙嫌酸正丁 _(n-butyl 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） --------{—裝------訂--：--7-7--ί 冰 • / 1*> (請先閱讀背面之注意事項再填寫本頁) 經濟部中夬標準局員工消費合作社印製 A7 B7 i、發明説明（6 ) acrylate)，丙嫌酸乙己酷（2-ethyl hexyl acrylate)， 甲基丙酸酯（methacrylate)，苯二酸二稀丙酷 （diallyl phthalate)，富馬酸二嫌丙酷（diallyl fumarate)，乙酸 乙烯酯（vinyl acetate)等，用置約為不飽和聚酯之10〜 40% ;除此之外必須加人抑制劑如氣錫（hydroquinone) ，苯 IS (benzoquinone)， 1,4 赛腿（1，4 naphthoquinone) ，2,5 —二苯基一對一苯醜（2，5-diphenyl-p-benzoquinone )，對一待一 丁基焦兒赛酣（p-tert-butylpyrocatechol) 等，用量為20-100 ppb。 本發明製得K条不飽和聚酯黏度在300-3000原泊，分 子量為1000-4000 ,物性符合一般不飽和聚酯產品需求， 並可應用於不同加工方式而能製成各種用途之難燃防火塑 膠製品。 有關本發明所採用之技術及方法，玆舉例説明於后， 相信本發明之目的、特擻及製法優點，當可由之得一深入 而具體的瞭解，這些實施例僅予實質的説明，但本發明之 内容並不限於所舉之實施例。 實施例一： 一個四頸反應瓶，其上裝設攪拌棒，分餾冷凝管，氮 氣閥，反應瓶外圍以加熱包包圍加熱，反應前抽真空除氣 ，再導入氮氣流，並預熱反應槽至1001C , 然後同時加入 216g馬來酐，133g駄酸酐，112g甲基膝酸二甲酯，375g丙 二醇，0 . 9 2 g I r g a η ο X 1 2 2 2 , 0 . 9 2 g 草酸錫，1 · 3 9 g 對一甲 苯碌酸（p-toluene sulfonic acid),加熱至 155*0 並進行 本紙張尺度適用中國國家標隼（CNS ) Α4規格（210Χ297公釐〉 (請先閱讀背面之注意事項再填寫本頁) 上，裝·(diethyl aethane phosphonate) > diaethyl ethane phosphonate »dipropyl ethane phosphonate fdi (di propy 1 butanephosph ο nate), diisobuty 1 benzenephosph ο nate , Benzene transfer acid diphenyl benzene (diphenyl benzene phosphonate) and other discic acid _ compounds. This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) -------- {— 装 ——- --- Subscribe--Ί — ^-«--- {冰 *»-*-_ (please read the notes on the back before filling out this page) / / Printed A7 B7 by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of the invention (4) The dibasic acid, diacid anhydride and dibasic enzyme used in the present invention are commonly used compounds for unsaturated polyesters, in which the saturated dibasic acid is orthophthalic acid (〇rth 〇phtha 1 ί cacid ), Phthalic acid gf (phtha 1 icanhydride), isophthalic acid (isophthalic acid), and tetrahydro phthalic acid (tetrahydro phthalic acid), hexahydrophtha 1 (ichydro acid) (hexahydrophtha 1 ic acid) Acid (tetra chlorophthal ic acid), adipic acid, diierized linseed oil and soybean oil fatty acid (soy bean oi 1 fa 11 yacid) and acid ffF (anhydride), etc .; unsaturated double bonds containing double bonds The metaacid is aaleic acid, naleic anhydride, fuaaric acid, itaconic acid, citraconic acid, and aesaconic acid. ), Aconic acid, etc .; binary enzymes are ethylene glycol, propylene glycol, dimethyl glycol, and dipropylene. glycol), 1-4 butanediol, 1-4 butanediol, neopentyl glycol, pentyl glycol, oxyalkylated bisphenol, hydrogenation Hjrdrogened bisphenols, etc. · Dibasic acids and binary enzymes can be used alone or in combination. The ratio of dibasic enzyme to dibasic acid required for the chemical reaction in the production method of the present invention is 1.03: 1.0 to 3.0: 1.0, and the ratio of saturated dibasic acid to dibasic acid containing double bonds is 0.05: 0.95 to 0.95: 0.05; The ratio of phosphorus compound to saturated dibasic acid is 0.05 ·· 0.95 to 0.95: 0.05, of which Phosphorus-6-This paper scale is applicable to China National Standard (CNS) A4 specification (2 丨 OX297mm) fvl ^ in 1L ^^ — ^ 1 ^^ 1 J 洚-:-(please read the precautions on the back before filling in this page) Order A7 ___B7_ printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention (5) The number of moles of the compound is from 0.1 to The phosphorus content of unsaturated polyester made from 0.7 is 0.1 to 10%. The effective catalyst combination used in the reaction process of the present invention is Jinyang catalyst combined with organic acid, wherein the organic gold hydrazone catalyst such as organotin alkoxide gasification compounds, for example, such as dibutyl tin oxide (dibutyl tin oxide) , Dibutyl tin acetate, tin chloride, tin oxalate, antimony oxide, Zinc oxide, good gasification ( calciu · oxide), etc., with a setting of 0.01-0. (relative to the use of all dibasic acids), and the most suitable amount range is 0.1-0.5%; organic acids such as p-toluene sulfonic acid (p-toulene su 1 f ο nicacid), sulfuric acid (su 1 f ο nicacid), hydrochloric acid (hyd "〇ge η chloride), bag acid (phosphoric acid), trichloride (phosphorus chloride), etc., * is 0.01-0.6 wt%, the most suitable amount 0.05-0.4¾ 〇 For suspected thermal stability in the course of the reaction, add heat stabilizer bribes such as hindered phenol (hinder Phenol) and use Dong as 0.01-0.5 vft% of dibasic acid. Saturated polyester is finally diluted with a reactive single plaque, which contains Vinyl functional groups such as styrene, methyl methacrylate, vinyl toluene, divinyl benzene, and methyl propionate (Methyl acrylate), ethyl acrylate, ethyl eethacrylate, n-butyl nethacrylate, n-butyl lethacrylate, N-butyl propionate_ (n-butyl) The paper size is in accordance with Chinese National Standard (CNS) Α4 specification (210Χ297mm) -------- {— 装 ------ 定-:- 7-7--ί 冰 • / 1 * > (please read the notes on the back before filling in this page) A7 B7 i, invention description (6) acrylate) printed by the Employee Consumer Cooperative of the Bureau of Standards and Statistics, Ministry of Economic Affairs, C 2-ethyl hexyl acrylate, methacrylate, diallyl phthalate, diallyl fumarate, vinyl acetate acetate), etc., use about 10 ~ 40% of unsaturated polyester; in addition, an inhibitor such as gas tin (hydroquinone) must be added ), Benzene IS (benzoquinone), 1,4 legs (1,4 naphthoquinone), 2,5-diphenyl one-to-one benzene ugly (2,5-diphenyl-p-benzoquinone), one to one to be a butyl Jiao'er P-tert-butylpyrocatechol, etc., the dosage is 20-100 ppb. The K-shaped unsaturated polyester prepared by the invention has a viscosity of 300-3000 original poises, a molecular weight of 1000-4000, physical properties that meet the needs of general unsaturated polyester products, and can be applied to different processing methods and can be made into a variety of flame-retardant applications Fireproof plastic products. Regarding the technology and method adopted by the present invention, the following examples are given. It is believed that the purpose, special features and advantages of the manufacturing method of the present invention can be gained a deep and specific understanding from these embodiments. The content of the invention is not limited to the cited embodiments. Example 1: A four-necked reaction bottle equipped with a stir bar, a fractionation condenser, a nitrogen valve, and the periphery of the reaction bottle is heated by a heating bag. Before the reaction, vacuum degassing, then introduce nitrogen flow, and preheat the reaction tank To 1001C, then add 216g of maleic anhydride, 133g of dianhydride, 112g of dimethyl methyl benzoate, 375g of propylene glycol, 0.92g I rga η ο X 1 2 2 2, 0.92 g tin oxalate, 1 · 3 9 g p-toluene sulfonic acid, heated to 155 * 0 and the paper size is applicable to China National Standard Falcon (CNS) Α4 specification (210Χ297mm) (Please read the note on the back first Please fill in this page again)
,1T 經濟部中央標準局負工消费合作社印装 A7 B7五、發明説明（7) 共聚合反應，反應約12小時，反醮過程中記錄酸價及皤出 物比率，酸價至70-90mg.KOH/g且酸價不再變化時，移去 分皤冷凝管，然後關閉氮氣，並抽低真空（至10 torr)約 2小時，再停止反應，如此可得無色透明磷条難燃不飽和 聚酯，所製得之磷条不飽和聚酯與苯乙烯以70/30比例摻 配，並加入40 pp氫醍，攪拌並溶解均勻，即得經反應性 單體稀釋之樹脂產品。 實施例二： 如實施例一之裝置及步驟，加入235g馬來酐，118g苯 二酸酐，99g甲基膝酸二甲酯，395g丙二酵，0.9g二丁 基錫氣化物，1 . 36 g對一甲苯磺酸，加熱至170 並進行共 聚合反應，反應約8-10小時，當酸價不再變化時，移去分 餾冷凝管，關閉氮氣並抽低真空1.5小時，将所製得之難 燃不飽和聚酯與苯乙烯以60/40比例摻配，並加人20 ppm 氫醍及20 ppm待一丁基兒茺酚，摻配均勻後即得產品。 實施例三： 如實施例一之裝置及步驟，加入323g馬來酐，133g苯 二酸酐，284g苯暖酸，186g乙二醇，242g丙二酵，1.48g 二 丁基錫氣化物，1.48g irganox 1010, 2.22g 硫酸，加 熱至160T：進行共聚合反應，至酸價不再變化，抽真空2 小時，將所製得之難燃不飽和聚酯與70/30的苯乙烯/甲 基丙烯酸甲酯混合單體以60/40比例摻配，並加入50ΡΡΠ 氫醍攪拌均勻即得含反應單體之難燃不飽和聚酯。 實施例四： 如實施例一之裝置及步驟，加入529g馬來酐，446g甲 -9 - (請先閲讀背面之注意事項再填寫本頁) -裝· 訂 本紙張尺度適用中國固家橾準（CNS ) A4規格（210X297公釐） A 7 .__ B7 五、發明説明（8 ) (請先閲讀背面之注意事項再填寫本頁) 基除酸二甲酯，614g乙二酵，1.95g氛化錫，1.95g鹽酸 ，反應性單《為50/50苯乙烯/甲基丙烯酸醋，與難燃不 飽和聚_摻配比例為35/65，並加入5βpp氳R。 比較例一 如實施例一之裝置及步®，加入539g馬來酐Ualeic a n h y d r i d e) » 6 6 6 g 苯二酸折（p h t h a 1 i c a n h y d r i d e)，114 0 g 丙二酵（propylene glycol) ，2.41g 氣化錫（tin chloride) ，反應性單體為苯乙烯（styrene),與所合成之不飽和聚 酯摻配比例為30/70。 本發明所製得之磷条難燃不飽和聚酯，經硬化處理製 得試Η ,按照ASTM D2863塑睡材料之限氣指數测試法之規 定測試燃燒性質，所得结果可見表一。 根據限氣指數測試標準，於限氣指數大於21卽有自熄 性質，由表中得知所合成之磷糸不飽和聚酯限氣指數均大 於21,並具有明顯之自熄性，與一般未經難燃處理之不飽 和聚酯（比較例一）比較，刖後者速低於21,其值只連18 ，並且遇火迅速燃燒，由此更顯示本發明之磷条不飽和聚 酯之難燃防火待性。 經濟部中央標準局貝工消費合作社印製 表一燃嬈性能測試 a號㈣ 限氣指數 自熄性* 實施例一 22 0 實施例二 22 0 實施例三 24 0 實施例四 26 0 比較例一 18 X -10 - 本紙張尺度適用中國國家標準（CNS ) ( 210X297公釐） # S ί晕糞詈癀性, 1T Printed A7 B7 by the Ministry of Economic Affairs Central Bureau of Standards Consumer Cooperatives V. Description of invention (7) Copolymerization reaction, about 12 hours of reaction, recording acid value and ratio of refractory products during reaction, acid value up to 70-90mg .KOH / g and the acid value no longer changes, remove the sub-condensation tube, then turn off the nitrogen, and evacuate the vacuum (to 10 torr) for about 2 hours, then stop the reaction, so that the colorless and transparent phosphor strip is difficult to burn Saturated polyester. The prepared phosphorous unsaturated polyester and styrene are blended at a ratio of 70/30, and 40 pp hydrogen hydride is added, stirred and dissolved uniformly to obtain a resin product diluted with reactive monomers. Example 2: As in the device and steps of Example 1, 235g maleic anhydride, 118g phthalic anhydride, 99g dimethyl methyl benzoate, 395g malonate, 0.9g dibutyltin vapor, 1.36g Toluene sulfonic acid, heated to 170 and copolymerized. The reaction takes about 8-10 hours. When the acid value no longer changes, remove the fractionation condenser, close the nitrogen and pull down the vacuum for 1.5 hours. Unsaturated polyester and styrene are blended at a ratio of 60/40, and 20 ppm of hydrogen bisphenol and 20 ppm of monobutyl cresol are added, and the product is obtained after blending evenly. Example 3: As in the device and steps of Example 1, 323g maleic anhydride, 133g phthalic anhydride, 284g benzene warm acid, 186g ethylene glycol, 242g malonate, 1.48g dibutyltin vapor, 1.48g irganox 1010 were added , 2.22g sulfuric acid, heated to 160T: copolymerization reaction, until the acid value no longer changes, evacuated for 2 hours, the prepared flame-retardant unsaturated polyester and 70/30 styrene / methyl methacrylate The mixed monomers are blended in a ratio of 60/40, and 50PPPI hydrogen hydride is added and stirred uniformly to obtain a flame retardant unsaturated polyester containing reactive monomers. Example 4: As in the device and steps of Example 1, add 529g maleic anhydride and 446g A-9-(please read the precautions on the back and then fill out this page)-the size of the book is applicable to China Gujiaju (CNS) A4 specification (210X297mm) A 7 .__ B7 V. Description of the invention (8) (please read the notes on the back before filling in this page) dimethyl acid-based dimethyl ester, 614g oxalase, 1.95g atmosphere Tin oxide, 1.95g hydrochloric acid, the reactive monomer is 50/50 styrene / methacrylic acid vinegar, the blending ratio with the flame retardant unsaturated poly_ is 35/65, and 5βpprR is added. The comparative example is the same as the device and step® of Example 1, adding 539g of maleic anhydride (Ualeic anhydride) »6 6 6 g phtha 1 icanhydride, 114 0 g propylene glycol, 2.41g gas Tin chloride, the reactive monomer is styrene, and the blending ratio of the synthesized unsaturated polyester is 30/70. The phosphorous flame retardant unsaturated polyester prepared by the present invention is hardened to obtain test H, and the combustion properties are tested according to the provisions of the ASTM D2863 Plastic Sleeping Material Gas Limit Index Test Method. The results can be seen in Table 1. According to the gas limit index test standard, when the gas limit index is greater than 21, it has self-extinguishing properties. From the table, it is known that the synthetic phosphorus phosphate unsaturated polyester has a gas limit index greater than 21, and it has obvious self-extinguishing properties, and Compared with the unsaturated polyester without flame retardant treatment (Comparative Example 1), the latter has a speed lower than 21, its value is only 18, and it burns rapidly in the event of fire, thus further showing the phosphorous unsaturated polyester of the present invention. Flame-retardant and fire-resistant. The Central Standards Bureau of the Ministry of Economic Affairs Beigong Consumer Cooperative Printed Table 1 Fuel Performance Test No. a (iv) Gas Limit Index Self-extinguishing * Example 1 22 0 Example 2 22 0 Example 3 24 0 Example 4 26 0 Comparative Example 1 18 X -10-This paper scale is applicable to the Chinese National Standard (CNS) (210X297mm) # S ί Halo feces