576829 A7 __BZ__ 五、發明說明（/ ) • I I---1 I —^^1 --- (請先閱讀背面之注意事項再填寫本頁) 本發明是關於以胍鹽爲主的殺生物聚合物’其係用作 爲醫學、獸醫學、污水處理、家用，以及所有需要殺生物 製劑之經濟體系中之殺菌劑。除此之外，本發明是關於一 種製造該鹽之方法。 本發明的目的是製造一種以胍鹽爲主、均勻且純之高 分子量消毒劑，其係具有低毒性但高度殺生物活性、較大 的相對莫耳質量、較高親水性、以及界面活性物質的特性 Ο 該胍衍生物之達成，係爲胍酸加成鹽與含有兩個胺基 和聚伸烷基鏈於其間之二胺的聚縮合反應之產物。 根據本發明來製造該產物，係在加熱的溫度，及取決 於所使用二胺的型式之9-16小時範圍之聚縮合反應期間， 在液態二胺的介質中，從反應的開始至其完成持續完全地 混合，使得該液態二胺暴露於與胍鹽之聚縮合反應。 根據本發明，在從合成的範圍中反應的開始至完成持 續完全地混合下，在液態中確保該反應的效能。因此’提 供該系統所需要的均勻性，在反應的製程中該試劑所需要 的莫耳關係的觀察’即’該產物的高品質，該製程用技術 裝備之促進’以及從如此製程所要求安全需要之促進。 特別是，將具有相對莫耳質量148之三甘醇二胺，以 及各種不同組成之聚氧伸烷基二胺，與該胍酸加成鹽反應 。如此，可以製造大量具有高活性且低毒性之聚陽離子本 質的殺生物聚合牧1 °可以特別將這些聚合物用於各種不同 用途之消毒劑° 3 ^ 張尺度適用中(CNS)aT規格^^297公釐) 576829 A7 _ B7_ 五、發明說明（3 ) 在20 °c室溫下，將25.28 g (0.17 mol)液態二胺-三甘醇 一《胺（TED A ) ( HaN-CHzCHa-O-CH^CHz-O- CH^CHrN^) 裝入具有 250 ml 容量且具備混合裝置及空 氣冷卻器之三頸活塞中。接著，將16.34 g (0.Π mol)粉 末鹽酸胍（GHC1)插入該活塞中。在持續完全混合下，將 該活塞加熱至150 °C溫度5小時的期間。取決於該反應的 進行，該反應介質的黏度平行增加於氣體形式氨的釋出。 在該製程狀態中，從該反應裝置取出試樣。該樹脂狀黃色 產物爲親水性且快速地完全稀釋於水中。將已秤重之該產 物的乾燥樣品（樣品la)稀釋於水中，並且利用烏伯婁德 黏度計（Ubbelohde-viscosimeter)來測量其特性黏度。結 果〔々〕=〇·〇4 dl/g證明：在該反應狀態中，已形成具有 該相對莫耳質量的平均重量Mw= 2500之聚合物產物。該 產物已具備殺生物特性（見表）。 接著，在170 °C溫度下，再繼續加熱9小時，同時完 全地混合該液體反應混合物。在此，該氣體生成和該反應 介質的黏度增加仍繼續。在上述的170 °C溫度下9小時的 反應時間之後’從該反應系統取出另一個試樣號碼lb)。 該聚合物試樣的顏色強度增加至淡棕色。該樣品lb)的特 性黏度之測量結果，得到値〔7?〕=0.07 dl/g，其關係於 該相對莫耳質量的平均重量Mw= 5800，其是指在該反應 進行期間，該相對莫耳質量增加。其殺菌性亦增加，見表 。因爲在170 °C溫度下·，在經過9小時期間的暴露之後， 仍觀察到氣體生成’即，該反應並未完成，所以在17〇。〇 5 1氏張尺度適用中國國家標準(CNS)A4 297公爱）----- ----I---------- (請先閱讀背面之注意事項再填寫本頁) 訂· 576829 A7 --------B7___ 五、發明說明（> ) 溫度下，再繼續加熱該反應系統4小時。接著，該氣體的 生成及反應完成。 最後，取出另一個聚合物樣品lc)並測量其特性黏度 値’〔7?〕= 0.085 dl/g，其符合相對莫耳質量Mw=9100 。該反應產物快速地完全稀釋於水中，並具有相當程度的 親水性。 測定該聚合物產物的個別元素成分，結果如下： 所測定之百分率：C_40.4 ; 40.25 ; N-19.7 ; 19.85 ; H-7.4 ; 7.456。 所計算 C7N302C1H16 之百分率：C-40.1 ; N-20.04 ； H-7.63 〇 因此，製造出新穎的聚合物產物，其組成符合聚三甘 醇鹽酸胍。製造出所敘述實驗的最終產物之產率爲98.7 %。其爲低毒性，對老鼠的口服劑量爲LD5G=3100 mg/kg ’即’具有比PHMG相當低的毒性（見表），以及高的殺 生物活性。 實施例2 : 如實施例1中相同的量和相同的莫耳關係，將同樣的 原始成分插入該反應活塞中。在持續完全混合下，在150 °C溫度下，從開始至完成該反應持續發生25小時期間直 到不再釋出氨。所得的反應產物爲水溶性，淡棕色且產率 99·1 %。該反應產物其元素之組成符合聚三甘醇鹽酸胍。 該元素之組成·· 所測定之百分率：C-40.7 ; Ν-19.65 ; Η-7.6。 6 ------------裝 i — (請先閱讀背面之注意事項再填寫本頁} 訂!- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 576829 A7 ________Β7__ 五、發明說明（女） 所計算之百分率：C-40.01 ; Ν-20.04 ; Η_7·63。 測量該樣品（樣品2)的特性黏度〔77〕=〇·11 (Mw = 11800)。該樣品具有比ΡΗΜ0較高的殺菌活性及較低 的毒性（見表）。 實施例3 : 在20 °C室溫下，將48 g ( 0.208 mol)液態聚氧伸丙 基二胺，及莫耳當量之19 g ( 0.208 mol)粉末鹽酸胍（ GHC1)插入具有250 ml容量且具備混合裝置及空氣冷卻 器之三頸活塞中；該液態聚氧伸丙基二胺具有下列結構： H2N-CH-CH2-[0-CH2-CH]x-NH2576829 A7 __BZ__ 5. Description of the invention (/) • I I --- 1 I — ^^ 1 --- (Please read the precautions on the back before filling this page) The present invention is about guanidinium-based biocides Polymers are used as bactericides in medicine, veterinary medicine, sewage treatment, households, and all economic systems that require biocides. In addition, the present invention relates to a method for producing the salt. The object of the present invention is to produce a homogeneous and pure high molecular weight disinfectant mainly based on guanidine salt, which has low toxicity but high biocidal activity, large relative molar mass, high hydrophilicity, and interfacial active substances. Properties 〇 This guanidine derivative is achieved by the polycondensation reaction of a guanidine acid addition salt with a diamine containing two amine groups and a polyalkylene chain in between. The production of the product according to the invention is at the heating temperature and during the polycondensation reaction in the range of 9-16 hours depending on the type of diamine used, in the medium of the liquid diamine, from the beginning of the reaction to its completion. Continue mixing completely so that the liquid diamine is exposed to a polycondensation reaction with a guanidinium salt. According to the present invention, the effectiveness of the reaction is ensured in a liquid state with continuous and complete mixing from the start to the completion of the reaction in the range of synthesis. Therefore 'providing the homogeneity required by the system, the observation of the mole relationship required by the reagent in the reaction process', that is, 'the high quality of the product, the promotion of the process with technical equipment' and the safety required from such a process Need for promotion. In particular, triethylene glycol diamine having a relative molar mass of 148, and polyoxyalkylene diamines of various compositions are reacted with the guanidine acid addition salt. In this way, it is possible to produce a large number of highly active and low-toxic polycationic biocide polymers. ° These polymers can be used as disinfectants for various applications. ° 3 ^ Applicable to CNS aT specifications ^^ 297mm) 576829 A7 _ B7_ V. Description of the invention (3) At room temperature of 20 ° C, 25.28 g (0.17 mol) of liquid diamine-triethylene glycol-amine (TED A) (HaN-CHzCHa-O -CH ^ CHz-O- CH ^ CHrN ^) In a three-neck piston with a capacity of 250 ml, a mixing device and an air cooler. Next, 16.34 g (0.Π mol) of powdered guanidine hydrochloride (GHC1) was inserted into the piston. The piston was heated to a temperature of 150 ° C for a period of 5 hours with continuous complete mixing. Depending on the progress of the reaction, the viscosity of the reaction medium increases in parallel with the release of ammonia in gaseous form. In this process state, a sample is taken out of the reaction device. The resinous yellow product was hydrophilic and quickly and completely diluted in water. A dry sample (sample la) of the weighed product was diluted in water, and its intrinsic viscosity was measured using an Ubbelohde-viscosimeter. The result [々] = 0.004 dl / g proves that in this reaction state, a polymer product having an average weight Mw = 2500 of the relative molar mass has been formed. The product is already biocidal (see table). Then, at 170 ° C, heating was continued for another 9 hours while the liquid reaction mixture was completely mixed. Here, the gas generation and the viscosity increase of the reaction medium continue. After a reaction time of 9 hours at the aforementioned temperature of 170 ° C, another sample number lb) was taken from the reaction system. The color intensity of the polymer sample was increased to light brown. As a result of measuring the intrinsic viscosity of the sample lb), 値 [7?] = 0.07 dl / g is obtained, which is related to the average weight of the relative molar mass Mw = 5800, which means that during the reaction, the relative molar Ear quality increases. Its bactericidal properties have also increased, see table. Because at a temperature of 170 ° C, after 9 hours of exposure, gas generation was still observed ', that is, the reaction was not completed, it was at 17 °. 〇5 1's scale is applicable to China National Standard (CNS) A4 297 Public Love) ----- ---- I ---------- (Please read the precautions on the back before filling this page ) Order · 576829 A7 -------- B7___ 5. Description of the invention (>) Continue to heat the reaction system for 4 hours at the temperature. Then, the generation and reaction of the gas are completed. Finally, take another polymer sample lc) and measure its intrinsic viscosity 値 ’[7?] = 0.085 dl / g, which corresponds to the relative molar mass Mw = 9100. The reaction product is rapidly and completely diluted in water and has a considerable degree of hydrophilicity. The individual elemental components of the polymer product were measured and the results were as follows: The measured percentages were: C_40.4; 40.25; N-19.7; 19.85; H-7.4; 7.456. Calculated percentages of C7N302C1H16: C-40.1; N-20.04; H-7.63 〇 Therefore, a novel polymer product was produced with a composition conforming to polytriethylene glycol guanidine hydrochloride. The yield of the final product from the described experiment was 98.7%. It is of low toxicity, and the oral dose to mice is LD5G = 3100 mg / kg, that is, it has considerably lower toxicity than PHMG (see table), and high biocidal activity. Example 2: The same original component was inserted into the reaction piston as the same amount and the same Mohr relationship as in Example 1. With continuous complete mixing, at a temperature of 150 ° C, the reaction continued for a period of 25 hours from the beginning to the completion until ammonia was no longer released. The obtained reaction product was water-soluble, light brown, and the yield was 99.1%. The reaction product has an elemental composition that conforms to polytriethylene glycol guanidine hydrochloride. Composition of this element · Measured percentages: C-40.7; Ν-19.65; Η-7.6. 6 ------------ install i — (Please read the precautions on the back before filling out this page} Order!-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 〉 576829 A7 ________ Β7__ 5. The percentage calculated by the invention description (female): C-40.01; Ν-20.04; Η_7 · 63. Measure the intrinsic viscosity of this sample (sample 2) [77] = 〇11 (Mw = 11800) This sample has higher bactericidal activity and lower toxicity than PBSM0 (see table). Example 3: 48 g (0.208 mol) of liquid polyoxypropylene diamine at 20 ° C room temperature, and Mol equivalent 19 g (0.208 mol) of powdered guanidine hydrochloride (GHC1) is inserted into a three-necked piston with a capacity of 250 ml and a mixing device and an air cooler. The liquid polyoxypropylene diamine has the following structure: H2N- CH-CH2- [0-CH2-CH] x-NH2
I I CH3 CH3 χ=2·6 其具有230莫耳重量。在持續完全混合下，加熱該混 合物’首先在150。(：溫度下2小時期間，然後在170 t 溫度下9小時期間。在該狀態中，從該反應混合物中取出 樣品3a)，其爲淡棕色、親水性、黏稠的產物，然後測量其 特性黏度〔77〕= 0.045 dl/g，其符合莫耳重量Mw=3000 °再者，在170 °C溫度下，再繼續加熱持續9小時期間直 到不再釋出氨，即，直到該反應完成。該最終產物的產率 爲 98.9 %。 根據該個別元素的分析資料，該最終產物符合聚氧伸 丙基鹽酸胍所欲的化學式。 所測定之百分率：C-50.85 ; Ν_13·35 ; H-9.6。 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------- (請先閱讀背面之注意事項再填寫本頁) 訂： 576829 A7 _______ B7____ 五、發明說明（石） 所計算之百分率·· C-50.4 ; N-13.57 ; Η-9·69。 測量該反應的最終產物，該樣品3b)的特性黏度〔7? 〕= 0.12，其符合該莫耳重量_Mw = 12500 ;即，較局方令 PHMG的莫耳重量。 樣品3b)之殺菌性的測定（E.coli，庫存號碼2590)， 顯示比PHMG較高的殺生物活性及較低的毒性（見表）。 實施例4 : 在 20 °C 室溫下，將 124.8 g ( 0.208 mol)，具有 600 莫耳重量之液態二胺-聚氧伸乙基二胺/聚氧伸丙基，及19 g ( 0.208 mol)鹽酸胍（GHC1)插入具有250 ml容量且具 備混合裝置及空氣冷卻器之三頸活塞中；該聚氧伸乙基二 胺/聚氧伸丙基具有下列結構式： CH3 CHb CHsI I CH3 CH3 χ = 2 · 6 It has a weight of 230 mol. With continuous thorough mixing, the mixture 'is first heated at 150 ° C. (: 2 hours at temperature, then 9 hours at 170 t. In this state, sample 3a is taken from the reaction mixture), which is a light brown, hydrophilic, viscous product, and then its intrinsic viscosity is measured [77] = 0.045 dl / g, which corresponds to a molar weight Mw = 3000 °, and at 170 ° C, heating is continued for another 9 hours until ammonia is no longer released, that is, until the reaction is complete. The yield of the final product was 98.9%. According to the analysis data of the individual elements, the final product conforms to the desired chemical formula of polyoxypropylguanidine hydrochloride. Measured percentage: C-50.85; N_13.35; H-9.6. 7 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) --------------- (Please read the precautions on the back before filling this page) Order: 576829 A7 _______ B7____ V. Calculated percentage of invention description (stone) C-50.4; N-13.57; Η-9 · 69. The end product of the reaction was measured. The intrinsic viscosity of the sample 3b) [7?] = 0.12, which corresponds to the Mohr weight _Mw = 12500; that is, the Mohr weight of PHMG is more than the local average. The bactericidal measurement of sample 3b) (E.coli, stock number 2590) showed higher biocidal activity and lower toxicity than PHMG (see table). Example 4: At room temperature of 20 ° C, 124.8 g (0.208 mol) of liquid diamine-polyoxyethylene diamine / polyoxypropylene with a weight of 600 mol, and 19 g (0.208 mol) ) Guanidine hydrochloride (GHC1) is inserted into a three-necked piston with a capacity of 250 ml and a mixing device and an air cooler; the polyoxyethylene diamine / polyoxypropylene has the following structural formula: CH3 CHb CHs
I I I H2NCHCH2-((X：HCH2)a-(0CH2CH2)b-(0CH2CH)c-NH2 a+c=2·5 ， b=8·5 〇 再者，在持續完全混合下，在150 °C溫度下加熱該反 應混合物25小時期間。在反應進行期間，發生氨的釋出及 該反應系統的黏度增加。在加熱25小時期間之後，不再釋 出氨，即，該反應完成。製造出該反應產物的產率99.1 % 。其爲快速地完全稀釋於水中之淡棕色聚合物。測量所 製得聚合物之特性黏度，即，樣品4 :〔 7/〕=0·13，其符 合莫耳重量Mw= 13500 ;即，首次以聚縮合反應來製造出 具有如此高莫耳質量之以鹽酸胍爲主的聚合物。 根據該個別元素分析的資料，所製得之聚合物產物聚 8 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 訂一 576829 A7 ____ B7 _ 五、發明說明（Π ) 氧伸乙基鹽酸胍符合上述的聚氧伸乙基結構基團。 所測定之百分率：C-53.1 ; N-7.85 ; H-6.95。 所計算之百分率·· C-52.3 ; · N_7.87 ; H-7.04。 所製得的聚合物具有較低的毒性及增強的殺菌性（見 表）。所製得的聚合物也具有明顯的界面活性聚合物之特 性。 已顯τρ:所測定該樣品之表面張力的値爲32 din/ch，其 接近於習知界面活性物質十二烷基硫酸鈉鹽之表面張力。 (應強調：在PHMG樣品中無法測定出明顯的界面活性特 性。）該界面活性物質的特性應使得在相分離界限時，對 於合成的聚合物產物之殺生物特性的發生更有效，尤其是 對於表面的處理（消毒）及其作爲淸潔劑中成分之利用。 實施例5 : 聚三甘醇磷酸二氫胍之製造。 在室溫下，將47.5 g ( 0.32 mol)液態三甘醇二胺（相 對莫耳質量148)插入具有250 ml容量且具備機械式混合 裝置及空氣冷卻器之三頸活塞中。接著，將50.24 g (0.32 mol)粉末磷酸二氫胍（相對莫耳貧量157)插入該活塞中 ，即，該試劑的莫耳關係爲1 : 1。將具有該液態反應物料 之活塞插入具備溫度調節器之油浴槽中。在持續混合下， 將該反應物料加熱至170 °C溫度11小時之內。從上述的 熱調節啓動的第一分鐘開始起，發生氨的強烈釋出（試紙 的變色），其證明聚縮合反應的進行。在該反應的進行期 間，該反應物料變濃稠，並且可以目視觀察到泡沫形成。 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -丨 I 丨 I I — I — I I · I I (請先閱讀背面之注意事項再填寫本頁) 訂-- 576829 A7 ____Β7__ 五、發明說明（） 該反應混合物漸漸變成其體積超過該原始液體混合物的體 積之白色樹脂。一旦完成氨氣的釋出，該反應也終止。在 將該活塞冷卻之後，藉由刮勺的幫助，將該聚合物樹脂從 活塞中移出，並且以硏缽磨成粉末；其具有比聚氧三甘醇 鹽酸胍較高之疏水性，但同時快速地溶解於水。該實驗所 得產率約爲84.5 g最終聚合物產物。在25 °C下，0.4 N之 氯化鈉水溶液中測量所製得聚合物之特性黏度。該黏度〔 77〕= 0.056 dl/g 〇 所製得聚合物的元素之分析： 所計算的<：7；^3〇6?1118:(：-30.99 %;>1_15.49°/〇;〇-35.42 % ; P-11.44 % ; H-6.64 % 〇 實測到：C-31.38 % ; N-15.25 % ; P-11.67 % ; H-6.49 % 。 該分析證明所製得聚合物與所需要結構之一致性。 試驗所製得聚合物的殺生物特性。測定對於兩種型式 的細菌，在單元中該最低抑制濃度的値（。在大 腸桿菌(E. coli)細菌的例子中値爲2.1 // g/ml ;在綠膿桿菌 的例子中爲6.2 #g/ml。如此證實所製得聚合物的高度殺 生物活性。也試驗該聚合物的一些毒理特性値，測定對於 老鼠之LD5G値（口服劑量）。其値爲32〇0 mg/kg證明該 聚合物的低毒性。 實施例6 : 聚三甘醇碳酸胍之製造。 在室溫下，將148 S ( 1 mo1)液態三甘醇二胺，並且 10 ----I I I---丨 --- (請先閲讀背面之注意事項再填寫本頁) !訂· 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公楚） 576829 A7 _B7 五、發明說明（？） 接著將121 g ( 1 mol)粉末碳酸胍插入具有1 1容量且具備 機械式混合裝置及空氣冷卻器之三頸活塞中。在持續完全 混合下，將該活塞在油浴槽中加熱；在此，產生相當均勻 混合的試劑。在140 °C溫度下開始具有氨的釋出之強烈反 應。將該原始混合物維持在該溫度（140 °C ) 15小時的期 間。接著其變濃稠，並且轉變成其體積相當地超過該原始 反應物料的體積之泡沬形狀淡黃色物料。在將該活塞冷卻 之後，藉由刮勺的幫助，將該聚合物樹脂從其中移出，並 且以硏缽磨成淡色粉末；其具有相當高度之疏水性。該試 驗的結果，製造出約232 g具有特性黏度〔7?〕=0.065 dl/g (在25 °C下，（MN之NaCl水溶液中所測得），有限 度水溶性之聚合物-聚三甘醇碳酸胍。 所製得聚合物的元素之分析： 所計算的 C8N305H17 : C-40.85 % ; N-17.87 % ; 0-34.04 % ; H-7.23 〇/〇 〇 實測到：041.31 °/〇 ; N-17.65 % ; H-7.03 %。 該分析證明該試驗的結果如期符合該計算。 測定所製得聚合物_聚三甘醇碳酸胍對於大腸桿菌 (E.coli)細菌之最低抑制濃度的値（//g/ml)。該最低抑制 濃度的値爲20 mg/ml證實所製得聚合物的殺生物活性。 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------裝—— (請先閱讀背面之注意事項再填寫本頁) 訂 576829 A7 B7 五、發明說明（π) 表 合成聚氧伸烷基鹽酸胍之特性 樣品 號碼 在 25 °C， 0.1 n NaCl溶液中 所測量 特性黏度 [η ] =dl/g 該相對莫耳 質量的平均 重量Mw= - 殺生物力 最低抑制濃度之百分 率（E-coli ， 庫存號碼2590) 毒性 □服劑量LD5〇 mg/kg (對老鼠） 原型 0.1 10000 0.0007 2500 la) 0.04 2500 0.003 lb) 0.07 5800 0.0015 lc) 0.085 9100 0.001 3000 2 0.11 11800 0.0003 3100 3a) 0.045 3000 0.002 * 3b) 0.12 12500 0.0001 3150 4 0.13 13500 0.00007 3250 ------------·裝—— (請先閱讀背面之注意事項再填寫本頁) 訂 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐）III H2NCHCH2-((X: HCH2) a- (0CH2CH2) b- (0CH2CH) c-NH2 a + c = 2 · 5, b = 8 · 5 〇 Furthermore, under continuous and complete mixing, at a temperature of 150 ° C The reaction mixture was heated for a period of 25 hours. During the reaction, ammonia release occurred and the viscosity of the reaction system increased. After heating for 25 hours, ammonia was no longer released, that is, the reaction was completed. The reaction was produced The yield of the product is 99.1%. It is a light brown polymer that is rapidly and completely diluted in water. The intrinsic viscosity of the polymer obtained is measured, that is, sample 4: [7 /] = 0.13, which corresponds to the molar weight Mw = 13500; that is, for the first time, a polymer based on guanidine hydrochloride with such a high molar mass was produced by a polycondensation reaction. According to the data of this individual element analysis, the polymer product obtained was 8 paper sizes Applicable Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page) Binding a 576829 A7 ____ B7 _ V. Description of the invention (Π) Oxandine guanidine hydrochloride meets Polyoxyethylene group mentioned above. Measured percentage: C-53.1 N-7.85; H-6.95. Calculated percentages ·· C-52.3; · N_7.87; H-7.04. The polymer produced has lower toxicity and enhanced bactericidal properties (see table). The prepared polymer also has obvious characteristics of interfacially active polymers. It has been shown that τρ: The surface tension of the sample measured is 32 din / ch, which is close to the conventional interfacial active substance dodecyl sulfate Surface tension. (It should be emphasized that obvious interfacial activity characteristics cannot be determined in PHMG samples.) The properties of the interfacial active material should be such that the biocidal properties of the synthesized polymer product occur more effectively at the phase separation limit Especially for surface treatment (disinfection) and its use as a detergent. Example 5: Production of polytriethylene glycol dihydrogen guanidine. At room temperature, 47.5 g (0.32 mol) of liquid trihydrate Glycol diamine (relative molar mass 148) was inserted into a three-necked piston with a capacity of 250 ml and a mechanical mixing device and air cooler. Next, 50.24 g (0.32 mol) of powdered diguanidine phosphate (relative molar) Lean 157) inserted into the piston That is, the Mohr relationship of the reagent is 1: 1. The piston with the liquid reaction material is inserted into an oil bath with a temperature regulator. The reaction material is heated to a temperature of 170 ° C within 11 hours under continuous mixing. From the first minute of the start of the above-mentioned thermal regulation, a strong release of ammonia (discoloration of the test paper) occurs, which proves the progress of the polycondensation reaction. During the progress of the reaction, the reaction material becomes thick and can be The formation of foam was visually observed. 9 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)-丨 I 丨 II — I — II · II (Please read the precautions on the back before filling this page) Order-576829 A7 ____ Β7__ 5. Description of the invention () The reaction mixture gradually becomes a white resin whose volume exceeds the volume of the original liquid mixture. Once the ammonia gas is released, the reaction is also terminated. After the piston is cooled, the polymer resin is removed from the piston with the help of a spatula and ground into a mortar; it has a higher hydrophobicity than polyoxytriethylene glycol guanidine hydrochloride, but at the same time Dissolves quickly in water. The yield from this experiment was about 84.5 g of the final polymer product. The intrinsic viscosity of the prepared polymer was measured in a 0.4 N aqueous solution of sodium chloride at 25 ° C. The viscosity [77] = 0.056 dl / g. Analysis of the elements of the polymer produced: Calculated <:7; ^ 3〇6? 1118: (: -30.99%; > 1_15.49 ° / 〇 〇-35.42%; P-11.44%; H-6.64% The consistency of the structure. The biocidal properties of the polymer produced by the test. The lowest inhibitory concentration of 値 in the unit was determined for the two types of bacteria. In the case of E. coli bacteria, 値 is 2.1 // g / ml; 6.2 # g / ml in the case of Pseudomonas aeruginosa. This confirms the high biocidal activity of the prepared polymer. Some toxicological properties of the polymer were also tested. LD5G was determined for mice値 (oral dose). Its 値 is 3200 mg / kg to demonstrate the low toxicity of the polymer. Example 6: Production of polytriethylene glycol guanidine carbonate. At room temperature, 148 S (1 mo1) liquid three Glycol Diamine, and 10 ---- II I --- 丨 --- (Please read the precautions on the back before filling this page)! Order · This paper size applies to China National Standard (CNS) A4 specifications ( 21〇x 297) 576829 A7 _B7 V. Description of the Invention (?) 121 g (1 mol) of powdered guanidine carbonate is then inserted into a three-necked piston with a capacity of 11 and a mechanical mixing device and an air cooler. The piston is heated in an oil bath with continuous complete mixing; here, a fairly uniformly mixed reagent is produced. A strong reaction with ammonia release begins at a temperature of 140 ° C. The original mixture is maintained at this temperature (140 ° C) for a period of 15 hours. Then it thickens and transforms into a bubble-like light yellow material whose volume considerably exceeds the volume of the original reaction material. After cooling the piston, with the help of a spatula, The polymer resin was removed therefrom and ground into a light-colored powder with a mortar; it has a relatively high degree of hydrophobicity. As a result of this test, about 232 g with an intrinsic viscosity [7?] = 0.065 dl / g (in At 25 ° C, (measured in NaCl aqueous solution of MN), a limited water-soluble polymer-polytriethylene glycol guanidine carbonate. Analysis of the elements of the prepared polymer: Calculated C8N305H17: C-40.85% ; N-17.8 7%; 0-34.04%; H-7.23 〇 / 〇 〇 Found: 041.31 ° / 〇; N-17.65%; H-7.03%. This analysis proves that the results of this test meet the calculation as scheduled. The lowest inhibitory concentration of the polymer, polytriethylene glycol guanidine carbonate on E. coli bacteria, was determined (// g / ml). The lowest inhibitory concentration of rhenium of 20 mg / ml confirmed the biocidal activity of the polymer produced. 11 This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ------------ installed—— (Please read the precautions on the back before filling this page) Order 576829 A7 B7 V. Description of the invention (π) Table Characteristic of synthetic polyoxyalkylene guanidine hydrochloride Sample No. Intrinsic viscosity measured at 25 ° C, 0.1 n NaCl solution [η] = dl / g Average of the relative molar mass Weight Mw =-Percentage of minimum biocidal inhibitory concentration (E-coli, inventory number 2590) Toxicity □ LD50 mg / kg (for mice) Prototype 0.1 10000 0.0007 2500 la) 0.04 2500 0.003 lb) 0.07 5800 0.0015 lc) 0.085 9100 0.001 3000 2 0.11 11800 0.0003 3100 3a) 0.045 3000 0.002 * 3b) 0.12 12500 0.0001 3150 4 0.13 13500 0.00007 3250 ------------ Installation-- (Please read the precautions on the back first (Fill in this page again) Order 12 paper sizes for China National Standard (CNS) A4 (210 x 297 mm)