201043642 六、發明說明： 【發明所屬之技術領域】 儲存^發明有關於一種乙稀基醋樹脂或不飽和聚酯樹脂的 :法’ _是有關於—種可增加乙烯基賴脂或不飽 和旨储存壽命的方法。 【先前技術】 ^由於乙烯基酯樹脂或不飽和聚酯樹脂分子結構中的碳 =飽和雙鍵’很容易會受到乙烯基賴脂或不飽和聚醋 1月曰内所含的雜質或是貯存乙縣喊脂或不飽和聚醋樹 知之環境溫度影響，而使得碳碳不飽和雙鍵開鍵，進而產 生自由基並進行連鎖聚合反應。並且，當溫度愈高或是乙 烯基月曰或不飽和聚酯樹脂貯存量愈大時，碳碳不飽和 雙鍵自行聚合的連鎖反應會更容易發生且反應也會更劇 烈，從而造成乙烯基酯樹脂或不飽和聚酯樹脂在運輸過程 》 或一般貯存時因前述反應而出現膠化現象，導致乙烯基酯 樹脂或不飽和聚酯樹脂無法使用而造成金錢上的損失。 以往改善此種問題所採取的方法，多是將自由基抑制 劑添加至乙稀基酯樹脂或不飽和聚酯樹脂中，以降低碳碳 不飽和雙鍵自行聚合的反應，從而延長乙烯基酯樹脂或不 飽和聚酯樹脂的貯存壽命，然而，抑制劑的添加卻會影響 乙烯基酯樹脂或不飽和聚酯樹脂的反應性，例如使乙婦基 酯樹脂或不飽和聚酯樹脂加工操作的時間增長，導致整個 製程過程耗費更多時間，或是乙烯基酯樹脂或使不飽和聚 3 201043642 酯樹脂無法硬化致使製成品強度不符標準，從而不當地提 高產品的不良率。而且若是抑制劑的添加量過多，則乙烯 基酯樹脂或不飽和聚酯樹脂硬化後的顏色會變深，進而使 得製成品的顏色過深而影響產品的外觀。 此外，亦有將乙烯基酯樹脂或不飽和聚酯樹脂於運輸 過程或貯存中皆置放於冷凍櫃中，以降低乙烯基酯樹脂或 不飽和聚酯樹脂之碳碳不飽和雙鍵的反應活化能，從而延 長乙稀基醋樹脂或不飽和聚醋樹脂的貯存壽命。然而，由 於此方法耗費的成本過高，因而不當地導致乙烯基酯樹脂 或不飽和聚酯樹脂的售價提高。 【發明内容】 有鑑於此，本發明之主要目的在於提供一種在運輸與 貯存乙稀基醋樹脂或不飽和聚醋樹脂時，可增加其儲存壽 命的方法。該方法具有提高該乙烯基酯樹脂或不飽和聚酯 樹脂中含氧量的步驟。如此H乙烯基崎脂或不飽 和聚酯樹脂中的碳碳不飽和雙鍵，因貯存溫度或是乙烯基 酯樹脂或不飽和聚酯樹脂内本身所含雜質影響而開鍵產生 ，由基時，氧氣即可與自*基反應從*產生較為穩定的過 氧化自由基，t自由基被氧氣雜後，乙絲s旨樹脂或不 飽和聚酯樹脂的自聚合反應即可減緩或完全停止，進而降 低乙烯基酯樹脂或不飽和聚酯樹脂在長時間運輸或貯存時 發生膠化現象的機率，最終可減少金錢的損失。 為達成上述目的，本發明可將含氧氣體加至該乙烯基 201043642 酯樹脂或不飽和聚酯樹脂中。並且，該含氧氣體可透過一 馬達或一注射針頭導入該乙烯基酯樹脂或不飽和聚酯樹脂 中0 此外’本發明亦可經由複數個化學物質進行反應而產 生氧氣至該乙烯基酯樹脂或不飽和聚酯樹脂中。並且，該 等化學物質係可添加至該乙烯基酯樹脂或不飽和聚酯樹脂 中0 在本發明一較佳實施例的方法中，可先將該含氧氣體 充填至-第-容n内，㈣再將該絲有該含氧氣體之第 -容器置放於-贿有該乙絲g旨樹脂或雜和聚醋樹脂 的第二容器内。 尸本方法中，該含氧氣體可為92%的純氧氣。然而，該 含乳氣體並無敎限制’例如該含氧氣體可為—般的空氣。 在本毛明另較佳實施例的方法中，可先將該等化學 〇 帛―容11置放於—儲存有該乙職S旨樹脂或不飽和聚酯樹 脂的第二容器内。201043642 VI. Description of the invention: [Technical field to which the invention pertains] Storage ^Inventives relating to a vinyl-based vinegar resin or an unsaturated polyester resin: the method ' _ is related to - a type of vinyl linoleum or unsaturated The method of storing the life. [Prior Art] ^Because the carbon=saturated double bond in the molecular structure of the vinyl ester resin or the unsaturated polyester resin is easily exposed to impurities or storage in the vinyl linoleum or unsaturated polyester vinegar in January In the county, the fat or unsaturated polychlorinated tree knows the environmental temperature, so that the carbon-carbon unsaturated double bond opens, and then generates free radicals and carries out chain polymerization. Moreover, when the temperature is higher or the storage amount of vinyl ruthenium or unsaturated polyester resin is larger, the chain reaction of self-polymerization of carbon-carbon unsaturated double bonds is more likely to occur and the reaction is more intense, thereby causing vinyl The ester resin or the unsaturated polyester resin gels due to the aforementioned reaction during transportation or general storage, resulting in a loss of money due to the inability of the vinyl ester resin or the unsaturated polyester resin to be used. In the past, the methods used to improve such problems were mostly to add a free radical inhibitor to a vinyl ester resin or an unsaturated polyester resin to reduce the self-polymerization of carbon-carbon unsaturated double bonds, thereby extending the vinyl ester. The storage life of the resin or unsaturated polyester resin, however, the addition of the inhibitor may affect the reactivity of the vinyl ester resin or the unsaturated polyester resin, for example, the processing operation of the ethyl ester resin or the unsaturated polyester resin. The increase in time leads to more time spent on the entire process, either the vinyl ester resin or the inability to harden the unsaturated poly 3 201043642 ester resin, resulting in a substandard product strength that unduly increases the product's defect rate. Further, if the amount of the inhibitor added is too large, the color of the vinyl ester resin or the unsaturated polyester resin after curing becomes deep, and the color of the finished product is too deep to affect the appearance of the product. In addition, vinyl ester resin or unsaturated polyester resin is placed in the freezer during transportation or storage to reduce the reaction of carbon-carbon unsaturated double bonds of vinyl ester resin or unsaturated polyester resin. The activation energy, thereby prolonging the storage life of the ethylene-based vinegar resin or the unsaturated polyester resin. However, the cost incurred by this method is too high, which unduly leads to an increase in the selling price of the vinyl ester resin or the unsaturated polyester resin. SUMMARY OF THE INVENTION In view of the above, it is a primary object of the present invention to provide a method for increasing the shelf life of a vinyl acetate resin or an unsaturated polyester resin when transporting and storing it. This method has a step of increasing the oxygen content in the vinyl ester resin or the unsaturated polyester resin. The carbon-carbon unsaturated double bond in the H vinyl-saturated or unsaturated polyester resin is opened due to the storage temperature or the influence of impurities contained in the vinyl ester resin or the unsaturated polyester resin. Oxygen can react with the self-purification reaction to generate a relatively stable peroxidation radical. When the t radical is dissolved by oxygen, the self-polymerization reaction of the resin or the unsaturated polyester resin can be slowed down or completely stopped. Further, the chance of gelation of the vinyl ester resin or the unsaturated polyester resin during long-term transportation or storage is reduced, and finally the loss of money can be reduced. To achieve the above object, the present invention can add an oxygen-containing gas to the vinyl 201043642 ester resin or unsaturated polyester resin. Moreover, the oxygen-containing gas can be introduced into the vinyl ester resin or the unsaturated polyester resin through a motor or an injection needle. Further, the present invention can also react to generate oxygen to the vinyl ester resin through a plurality of chemical substances. Or unsaturated polyester resin. Moreover, the chemical substances may be added to the vinyl ester resin or the unsaturated polyester resin. In a method of a preferred embodiment of the present invention, the oxygen-containing gas may be first filled into the -first volume. (4) placing the first container having the oxygen-containing gas in the second container in which the resin or the miscellaneous resin is mixed. In the cadaveric method, the oxygen-containing gas may be 92% pure oxygen. However, the milk-containing gas has no enthalpy limit. For example, the oxygen-containing gas may be air. In the method of another preferred embodiment of the present invention, the chemical 帛 帛 容 11 can be placed in a second container in which the resin or unsaturated polyester resin is stored.
化氫與二氧化錳。 本方法中，言 ^勿質裝人第-谷器内，爾後再將該製有該等化學物質之 丨I刺’只要是能夠經由化學 例如該等化學物質可為過氧 至· 1 : 0.001。 3亥過氧化妈與曱基兩烯酸的比例為1: 5 201043642 本發月增加乙稀基I旨樹脂或不飽和聚g旨樹脂儲存壽命 之方法，不僅能夠改善以往因抑制劑添加過多所導致之乙 烯基酯樹脂或不飽和聚酯樹脂無法硬化或是製成品顏色過 /木的缺失，且由於含氧氣體的價格較低，因此相較於使用 饧格叩貝之抑制劑或冷凍櫃的習知方法，本發明亦能有效 的降低耗費成本。 【實施方式】 現將本發明詳細說明於後。 依據本發明所提供之一種增加乙烯基酯樹脂或不飽和 聚酉曰樹脂在運輸過程或貯存時儲存壽命的方法，係具有提 南s亥乙烯基酯樹脂或不飽和聚酯樹脂中含氧量的步驟。藉 此，使氧氣可與因乙烯基酯樹脂或不飽和聚酯樹脂之碳碳 不飽和雙_鍵所產生的自由基反應，產生較為穩定的過 氧化自由基，以減緩或終止乙烯基酯樹脂或不飽和聚酯樹 脂的自聚合反應，進而降低膠化現象的發生機率。 在本發明的方法中，係可透過將含氧氣體加至乙烯基 酯樹脂或不飽和聚酯樹脂中來提高乙烯基酯樹脂或不飽和 聚酯樹脂巾的含氧量；或者是，可透過複數個化學物質進 行反應而產生氧氣至乙烯基酯樹脂或不飽和聚酯樹脂中。 更具體而言’本發明一較佳實施例係先將含氧氣體充 填至第一谷器内，然後再將充填有含氧氣體的第一容器置 放於儲存有乙烯基酯樹脂或不飽和聚酯樹脂的第二容器 内，使第-容!！_含氧氣體慢慢擴散至⑽絲樹脂或 201043642 不飽和聚醋樹脂中，從而提高乙焊基醋樹脂或不飽和聚醋 樹腊中的氧氣含量。 本實施例中’該含氧氣體可為92%的純氧氣。但並不 以此為限，例如該含氧氣體亦可為一般的空氣。 依據本發明另-較佳實施例，其係先將該等化學物質 I人m内’然後再將裝有該等化學物質的第一容器 置放於儲存有乙烯基酯樹脂或不飽和聚酯樹脂的第二容器 内’使第-容器内的含氧氣體慢慢擴散至乙烯基醋樹脂或 ° +飽和㈣樹脂中，從而提高乙稀基醋樹脂或不飽和聚酯 樹脂中的氧氣含量。 本實施例巾’料化學物質可為過氧簡與曱基丙婦 酸。但並不卩此為F艮’舉凡能夠經由化學反應而產生氧氣 的化學物質皆可使用，例如該等化學物質亦可為過氧化氫 與二氧化鐘。 1 本實施例中，該過氧化鈣與甲基丙烯酸的比例為1 : 2 、至 1 : 0.001。 'Hydrogen and manganese dioxide. In the method, it is possible to use the chemical substance such as the chemical substance, as long as it can be peroxygen to 1 : 0.001. . The ratio of the 3 oxidized mother to the decyl enoate is 1: 5 201043642 The method of increasing the storage life of the resin or the unsaturated polyg resin in the month of the month can not only improve the excessive addition of inhibitors in the past. The resulting vinyl ester resin or unsaturated polyester resin cannot be hardened or the color of the finished product is over/wood, and because of the lower price of the oxygen-containing gas, it is compared to the inhibitor or freezer using 饧格叩贝The conventional method of the present invention can also effectively reduce the cost. [Embodiment] The present invention will now be described in detail. According to the present invention, a method for increasing the storage life of a vinyl ester resin or an unsaturated polyfluorene resin during transportation or storage is characterized by having an oxygen content in a vinyl ester resin or an unsaturated polyester resin. A step of. Thereby, oxygen can be reacted with a radical generated by a carbon-carbon unsaturated double-bond of a vinyl ester resin or an unsaturated polyester resin to produce a relatively stable peroxidic radical to slow or terminate the vinyl ester resin. Or self-polymerization of unsaturated polyester resin, thereby reducing the probability of occurrence of gelation. In the method of the present invention, the oxygen content of the vinyl ester resin or the unsaturated polyester resin towel can be increased by adding an oxygen-containing gas to the vinyl ester resin or the unsaturated polyester resin; or, A plurality of chemicals are reacted to produce oxygen to the vinyl ester resin or the unsaturated polyester resin. More specifically, in a preferred embodiment of the present invention, an oxygen-containing gas is first filled into the first trough, and then the first container filled with the oxygen-containing gas is placed in the storage of the vinyl ester resin or unsaturated. In the second container of polyester resin, make the first volume!! _ Oxygen-containing gas is slowly diffused into (10) silk resin or 201043642 unsaturated polyacetate resin to increase the oxygen content in the ethylene-based vinegar resin or unsaturated polyester vinegar. In the present embodiment, the oxygen-containing gas may be 92% pure oxygen. However, it is not limited thereto. For example, the oxygen-containing gas may be ordinary air. According to another preferred embodiment of the present invention, the chemical substances are first placed in the first place, and then the first container containing the chemical substances is placed in the storage of the vinyl ester resin or the unsaturated polyester. In the second container of the resin, the oxygen-containing gas in the first container is slowly diffused into the vinyl vinegar resin or the ++ saturated (tetra) resin, thereby increasing the oxygen content in the ethylene-based vinegar resin or the unsaturated polyester resin. The material of the present embodiment may be peroxygen and thioglycolic acid. However, it is not necessary to use a chemical substance which can generate oxygen by a chemical reaction. For example, the chemical substance may be hydrogen peroxide or a second oxidation clock. 1 In this embodiment, the ratio of the calcium peroxide to methacrylic acid is 1:2 to 1:0.001. '
J 在本發明中，亦可利用馬達或一注射針頭將含氧氣體 導入乙烯基酯樹脂或不飽和聚酯樹脂中來提高乙烯基酯樹 脂或不飽和聚酯樹脂内的氧氣含量。 曰 在本發财’亦可將鱗化學物f添加至乙歸基酿樹 脂或不飽和聚酯樹脂中，待該等化學物質進行化學2應 時，即可在乙烯基酯樹脂或不飽和聚酯樹脂内產生氧氣W 從而提高乙烯基酯樹脂或不飽和聚酯樹脂内的氧氣含量。 7 201043642 兹舉以下範例進-步_本發明，誠該等範例僅用 以更加瞭解本發明，㈣用以關本發明的範圍，凡是所 屬技術領域巾具有通常知識者，在不違反本發明創作精神 下所為之各種變化與修飾均俱屬本發明之範_。 『氧氣含量對乙烯基酯樹脂或不飽和聚酯樹脂儲存壽 命的影響』 ~ <範例1> 將400克的乙烯基酯樹脂（BpA type vinyl⑽沉， SW 901 ’上緯企業股份有限公司供售）置於5〇〇毫升的玻 璃錐形瓶中，不通入任何氣體，之後將錐形瓶密封並儲存 於溫度78°C的條件下。 <範例2> 除了將通有空氣的軟管***乙烯基酯樹脂溶液内5分 鐘後，將錐形瓶密封，且每天都通5分鐘空氣之外，其餘 均與範例1相同。 <範例3> 除了將150克的乙烯基酯樹脂置於25〇毫升的玻璃錐 形瓶中之外，其餘均與範例1相同。 <範例4> 除了將150克的乙烯基酯樹脂置於250毫升的玻璃錐 形瓶中之外，其餘均與範例2相同。 <比較範例1> 除了將通有氮氣的軟管***乙烯基酯樹脂溶液内 分鐘之外’其餘均與範例1相同。 201043642 <比較範例2> 除了將通有氡氣的軟管***錐形瓶内，但不接觸乙烯 基酯樹脂溶液60分鐘之外，其餘均與範例丨相同。 <比較範例3> 除了將150克的乙婦基酯樹脂置於250毫升的玻璃錐 形瓶中，並將通有氮氣的軟管***乙烯基酯樹脂溶液内45 分鐘之外，其餘均與範例1相同。 <比較範例4> 〇 除了將150克的乙烯基酯樹脂置於250毫升的玻璃錐 形瓶中之外，其餘均與比較範例1相同。 <比較範例5> 除了將150克的乙烯基酯樹脂置於250毫升的玻璃錐 形瓶中之外，其餘均與比較範例2相同。 以上所述之「不通入任何氣體」，係指除了錐形瓶内原 本就具有的空氣之外，並不外加任何氣體。 ❹ 以上範例與比較範例的實驗結果，係顯示於下列表卜In the present invention, an oxygen-containing gas may be introduced into a vinyl ester resin or an unsaturated polyester resin by a motor or an injection needle to increase the oxygen content in the vinyl ester resin or the unsaturated polyester resin.曰In this Fortune' can also add the scaly chemical f to the ethyl ruthenium resin or unsaturated polyester resin. When the chemical substances are chemically responsive, they can be in the vinyl ester resin or unsaturated poly Oxygen gas is generated in the ester resin to increase the oxygen content in the vinyl ester resin or the unsaturated polyester resin. 7 201043642 The following examples are taken as follows: The present invention is only used to better understand the present invention, and (4) is used to clarify the scope of the present invention, and those who have ordinary knowledge in the technical field do not violate the invention. The various changes and modifications made under the spirit are all examples of the present invention. "Effect of oxygen content on storage life of vinyl ester resin or unsaturated polyester resin" ~ <Example 1> 400 g of vinyl ester resin (BpA type vinyl (10) sink, SW 901 ' Shangwei Enterprise Co., Ltd. for sale ) placed in a 5 〇〇 ml glass conical flask without any gas, and then the conical flask was sealed and stored at a temperature of 78 °C. <Example 2> The same as Example 1 except that the air-filled hose was inserted into the vinyl ester resin solution for 5 minutes, the conical flask was sealed, and air was passed for 5 minutes every day. <Example 3> The same as Example 1 except that 150 g of the vinyl ester resin was placed in a 25 cc glass conical flask. <Example 4> The same as Example 2 except that 150 g of the vinyl ester resin was placed in a 250 ml glass conical flask. <Comparative Example 1> The remainder was the same as in Example 1 except that the nitrogen-containing hose was inserted into the vinyl ester resin solution for a few minutes. 201043642 <Comparative Example 2> The procedure was the same as that of the example 除了 except that the helium-filled hose was inserted into the Erlenmeyer flask without being exposed to the vinyl ester resin solution for 60 minutes. <Comparative Example 3> Except that 150 g of the ethyl lactyl resin was placed in a 250 ml glass conical flask, and a nitrogen-containing hose was inserted into the vinyl ester resin solution for 45 minutes, the rest were Example 1 is the same. <Comparative Example 4> 〇 The same as Comparative Example 1 except that 150 g of the vinyl ester resin was placed in a 250 ml glass conical flask. <Comparative Example 5> The same as Comparative Example 2 except that 150 g of the vinyl ester resin was placed in a 250 ml glass conical flask. The phrase "no gas is introduced" as used above means that no gas is added except for the air originally contained in the conical flask.实验 The experimental results of the above examples and comparative examples are shown in the following table.
9 201043642 ，由表1的結果可明顯看出，當乙烯基酯樹脂内的氧氣 被通入的氮氣取代時’乙烯基醋樹脂的儲存壽命皆明顯降 低並且’直接將氮氣通入乙烯基酯樹脂溶液内之比較範 例1 3與4的乙埽基醋樹脂，其儲存壽命又更低於僅將氮 耽通至乙稀基醋樹脂溶液表面之比較範例2與5的乙稀基 醋樹脂。除此之外’當進一步將含有氧氣的空氣通入乙稀 基醋樹脂溶液内時（如範例2與4)，乙烯基醋樹脂的儲存 壽命即高於不通入任何氣體之範例！貞3的乙婦基醋樹 脂。因此可知，乙烯基_脂⑽含有的氧氣量係可直接〇 地影響乙烯基酯樹脂的儲存壽命。 r 『本發明之較佳實施例』 <範例5 > 先將2.2公斤的乙烯基酯樹脂裝入3公斤的鐵筒中， 然後將充填有92%純氧之250毫升的PE瓶置於前述3公 斤的鐵Λ中，之後將3公斤的鐵筒置入溫度6〇°c的烘箱中 以加速實驗。觀察不同時間後，乙烯基酯樹脂的膠化情況， 並同時以溶氧計偵測器（型號：CyberScanI)0 11()Meter， i) EUTCH INSTRUMENTS公司供售）檢測乙烯基酯樹脂内 的含氧量。 <範例6> 除了 250毫升的PE瓶内係裝有過氧化鈣(cdcium peroxide，Ca02)與甲基丙烯酸(methacrylic add, MAA)化合 物之外，其餘均與範例5相同。 <比較範例6> 201043642 除了 250毫升的ΡΕ瓶内係裴有250亳升的乙烯基酯 樹脂之外，其餘均與範例5相同。 以上範例與比較範例的實驗結果，係顯示於下列表2。 表2 Ο9 201043642 , it is apparent from the results of Table 1 that when the oxygen in the vinyl ester resin is replaced by the nitrogen introduced, the storage life of the vinyl vinegar resin is significantly reduced and the nitrogen gas is directly introduced into the vinyl ester resin. Comparative Examples 1 and 4 of the acetaminophen vinegar resin in the solution have a lower shelf life than the ethylene vinegar resins of Comparative Examples 2 and 5 which only pass the hydrazine to the surface of the ethylene vinegar resin solution. In addition, when the oxygen-containing air is further introduced into the ethylene vinegar resin solution (as in Examples 2 and 4), the storage life of the vinyl vinegar resin is higher than that without any gas!贞 3 of the Ethyl vinegar resin. Therefore, it is understood that the amount of oxygen contained in the vinyl ester (10) can directly affect the storage life of the vinyl ester resin. r "Preferred embodiment of the invention" <Example 5 > First, 2.2 kg of vinyl ester resin was charged into a 3 kg iron can, and then a 250 ml PE bottle filled with 92% pure oxygen was placed in the foregoing In the 3 kg iron shovel, a 3 kg iron cylinder was placed in an oven at a temperature of 6 ° C to accelerate the experiment. After observing the gelation of the vinyl ester resin at different times, the content of the vinyl ester resin was detected by a dissolved oxygen meter detector (Model: CyberScanI) 0 11 () Meter, i) EUTCH INSTRUMENTS Oxygen content. <Example 6> The same procedure as in Example 5 was carried out except that a 250 ml PE bottle was filled with a compound of cdcium peroxide (CaO 2 ) and methacrylic add (MAA). <Comparative Example 6> 201043642 The same as Example 5 except that the 250 ml bottle was filled with 250 liters of vinyl ester resin. The experimental results of the above examples and comparative examples are shown in Table 2 below. Table 2 Ο
3.81 ------丨（已膠化） 由表2的結果可明顯得知，隨貯存時間增加比較範 例6之乙烯基S旨樹脂内之含氧量逐漸減少，且至31天時就 已經完全膠化；另—方面，縱使範例6之乙烯基醋樹脂在 第20天時的含氧量低於比較範例6之乙埽絲樹脂，缺 而，範例6之乙晞基酉旨樹縫31科的含 : Ο 範例ό之乙烯基酯樹脂，且直 、比車乂 示於表2)。因此，本發明不直=效天:才f全膠化（未顯 或是以低溫冷咖二= 較於使用抑制劑 成本的優勢。 本發明更具有可降低3.81 ------丨 (glued) From the results of Table 2, it is apparent that the oxygen content in the resin of Comparative Example 6 is gradually decreased with the increase of storage time, and it is reduced to 31 days. Already completely gelled; on the other hand, even though the vinyl acetate resin of Example 6 has a lower oxygen content on the 20th day than the Ethyl silk resin of Comparative Example 6, the absence of the sample 6 The contents of the 31 family include: Ο The vinyl ester resin of the sample, and the straight and the rut are shown in Table 2). Therefore, the present invention is not straightforward: it is fully gelatinized (not shown or is low temperature cold coffee 2 = more advantageous than the cost of using an inhibitor. The present invention is more capable of being reduced