TW201806989A

TW201806989A - Polyvinyl chloride pipe

Info

Publication number: TW201806989A
Application number: TW106111432A
Authority: TW
Inventors: 麥克Ｔ佩特; 史帝文Ｒ拉帕奇
Original assignee: 羅門哈斯公司
Priority date: 2016-04-20
Filing date: 2017-04-05
Publication date: 2018-03-01
Also published as: TWI799376B

Abstract

The present invention relates to non-oriented and oriented polyvinyl chloride pipe comprising: (a) polyvinyl chloride; (b) from 2 to 5 parts by weight of polymeric processing aid per 100 parts by weight of the polyvinyl chloride; and (c) from 1.6 to 2.0 parts by weight percent of a paraffin wax per 100 parts by weight of the polyvinyl chloride. The polyvinyl chloride pipe of the present invention comprises a concentration of paraffin wax lubricant (> 1.5 parts per 100 parts polyvinyl chloride) heretofore unrecognized in the art, without the loss of key physical properties.

Description

聚氯乙烯管道 Polyvinyl chloride pipe

本發明係關於聚氯乙烯(PVC)管道，且特定而言，一種包括加工助劑及外部潤滑劑之PVC管道。 This invention relates to polyvinyl chloride (PVC) pipes and, in particular, to PVC pipes including processing aids and external lubricants.

定向聚氯乙烯(o-PVC)管道藉由在減小其重量時保持管道之爆裂強度及衝擊強度而提供相對於非定向PVC管道之顯著改良。可藉由以下製備o-PVC管道：以約一半所要最終直徑擠出非定向管道，隨後沿徑向將管道拉伸至約初始直徑的兩倍。所述製程提供減小約一半之管道壁厚及PVC鏈之相應對準(定向)，使PVC材料之強度提高。因此，o-PVC管道為常規PVC管道之約一半重量且需要一半原材料，同時保持強度或相對於非定向管道改良強度。 Directional polyvinyl chloride (o-PVC) pipes provide significant improvements over non-oriented PVC pipes by maintaining the burst strength and impact strength of the pipe while reducing its weight. The o-PVC pipe can be prepared by extruding the non-oriented pipe at about half of the desired final diameter and then radially stretching the pipe to about twice the original diameter. The process provides for a reduction in wall thickness of about half of the pipe and corresponding alignment (orientation) of the PVC chain to increase the strength of the PVC material. Thus, the o-PVC pipe is about half the weight of a conventional PVC pipe and requires half of the raw material while maintaining strength or improving strength relative to the non-oriented pipe.

雖然o-PVC相對於非定向PVC具有巨大改良，但製程之經濟因素使o-PVC遭遇阻礙。o-PVC通常在半分批製程中製得，其中將管道擠出，切割成段，加熱至100℃，且加壓擴張。所述製程中所需之勞動力及設備大大增加了o-PVC管道的成本。或者，可使用連續製程，其中使擠出之管道冷卻至100℃，且在心軸上拉伸。雖然成本較低，但連續製程僅可以擠壓製程之速率的三分之一進行，其受到在達成使管道直徑加倍所必需的充分應變之前PVC熔融物在拉伸期間發生斷裂的限制。 Although o-PVC has been greatly improved over non-oriented PVC, the economic factors of the process have made o-PVC suffer. o-PVC is typically produced in a semi-batch process in which the pipe is extruded, cut into sections, heated to 100 ° C, and pressurized to expand. The labor and equipment required in the process greatly increases the cost of the o-PVC pipe. Alternatively, a continuous process can be used in which the extruded tubing is cooled to 100 ° C and stretched on a mandrel. Although the cost is lower, the continuous process can only be carried out by one-third of the rate of the extrusion process, which is broken by the PVC melt during the stretching before the sufficient strain necessary to double the diameter of the pipe is achieved. Crack limit.

加工助劑為此項技術中已知的。舉例而言，美國專利第4,692,295號揭示某些用於達成熱塑性樹脂中之定向的PVC加工助劑，其含有乙烯基單體之均聚物或至少兩種乙烯基單體之共聚物。美國專利第6,391,976號揭示一種PVC泡沫加工助劑，其含有甲基丙烯酸甲酯與C₃-C₅甲基丙烯酸酯之粉末狀共聚物。 Processing aids are known in the art. For example, U.S. Patent No. 4,692,295 discloses certain PVC processing aids for achieving orientation in thermoplastic resins comprising a homopolymer of a vinyl monomer or a copolymer of at least two vinyl monomers. U.S. Patent No. 6,391,976 discloses a PVC foam processing aid comprising a powdered copolymer of methyl methacrylate and C ₃ -C ₅ methacrylate.

然而，需要研發提供改良之熔融強度及改良之調配物可加工性的PVC調配物，預期其將在PVC管道之連續拉伸中提供提高之操作速率。 However, there is a need to develop PVC formulations that provide improved melt strength and improved formulation processability, which is expected to provide increased operating rates in continuous stretching of PVC pipes.

在一個態樣中，本發明藉由提供一種非定向聚氯乙烯管道來解決所屬領域之需求，按管道重量計，所述管道包括：a)聚氯乙烯；b)每100重量份聚氯乙烯2至5重量份聚合加工助劑；及c)每100重量份聚氯乙烯1.6至2.0重量份外部潤滑劑；其中聚氯乙烯之K值介於60至75範圍內；其中聚合加工助劑包括50至95重量%甲基丙烯酸甲酯之結構單元及5至50重量%第二單體之結構單元，所述第二單體為C₂-C₆丙烯酸酯或C₂-C₆甲基丙烯酸酯或其組合；其中外部潤滑劑為多元醇酯或石蠟；且其中加工助劑之重量平均分子量介於5×10⁵道爾頓至5×10⁷道爾頓範圍內。 In one aspect, the present invention addresses the need in the art by providing a non-oriented polyvinyl chloride conduit comprising: a) polyvinyl chloride; b) per 100 parts by weight of polyvinyl chloride per pipe weight 2 to 5 parts by weight of the polymerization processing aid; and c) 1.6 to 2.0 parts by weight of the external lubricant per 100 parts by weight of the polyvinyl chloride; wherein the K value of the polyvinyl chloride is in the range of 60 to 75; wherein the polymerization processing aid comprises 50 to 95% by weight of a structural unit of methyl methacrylate and 5 to 50% by weight of a structural unit of a second monomer which is a C ₂ -C ₆ acrylate or a C ₂ -C ₆ methacrylic acid An ester or a combination thereof; wherein the external lubricant is a polyol ester or a paraffin wax; and wherein the processing aid has a weight average molecular weight ranging from 5 x 10 ⁵ Daltons to 5 x 10 ⁷ Daltons.

在另一態樣中，本發明為一種定向聚氯乙烯管道，按管道重量計，其包括：a)定向聚氯乙烯；b)每100重量份聚氯乙烯2至5重量份聚合加工助劑；及c)每100重量份聚氯乙烯1.6至2.0重量份外部潤滑劑；其中聚氯乙烯之K值介於60至75範圍內；其中聚合加工助劑包括50至95重量%甲基丙烯酸甲酯之結構單元及5至50重量%第二單體之結構單元，所述第二單體為C₂-C₆丙烯酸酯或C₂-C₆甲基丙烯酸酯或其組合；且其中外部潤滑劑為多元醇酯或石蠟；且其中加工助劑之重量平均分子量介於5×10⁵道爾頓至5×10⁷道爾頓範圍內。 In another aspect, the invention is a directional polyvinyl chloride pipe comprising, by weight of the pipe, a) oriented polyvinyl chloride; b) 2 to 5 parts by weight of polymeric processing aid per 100 parts by weight of polyvinyl chloride And c) 1.6 to 2.0 parts by weight of external lubricant per 100 parts by weight of polyvinyl chloride; wherein the K value of the polyvinyl chloride is in the range of 60 to 75; wherein the polymerization processing aid comprises 50 to 95% by weight of methacrylic acid esters of structural units, and 5 to 50 wt% of structural units of the second monomer, the second monomer is a C ₂ -C ₆ acrylate or methacrylate, C ₂ -C ₆ esters or combinations thereof; and wherein the external lubrication The agent is a polyol ester or a paraffin wax; and wherein the processing aid has a weight average molecular weight ranging from 5 x 10 ⁵ Daltons to 5 x 10 ⁷ Daltons.

本發明藉由在非定向PVC管道中提供加工助劑與石蠟之組合來解決需求，其使自非定向管道生產定向PVC管道之效率提高。 The present invention addresses the need by providing a combination of processing aids and paraffin in a non-oriented PVC pipe that increases the efficiency of producing directional PVC pipes from non-oriented pipes.

在第一態樣中，本發明為一種非定向聚氯乙烯管道，按管道重量計，其包括：a)聚氯乙烯；b)每100重量份聚氯乙烯2至5重量份聚合加工助劑；及c)每100重量份聚氯乙烯1.6至2.0重量份外部潤滑劑；其中聚氯乙烯之K值介於60至75範圍內；其中聚合加工助劑包括50至95重量%甲基丙烯酸甲酯之結構單元及5至50重量%第二單體之結構單元，所述第二單體為C₂-C₆丙烯酸酯或C₂-C₆甲基丙烯酸酯或其組合；其中外部潤滑劑為多元醇酯或石蠟；且其中加工助劑之重量平均分子量介於5×10⁵道爾頓至5×10⁷道爾頓範圍內。 In a first aspect, the invention is a non-oriented polyvinyl chloride pipe comprising, by weight of the pipe, a) polyvinyl chloride; b) 2 to 5 parts by weight of polymeric processing aid per 100 parts by weight of polyvinyl chloride And c) 1.6 to 2.0 parts by weight of external lubricant per 100 parts by weight of polyvinyl chloride; wherein the K value of the polyvinyl chloride is in the range of 60 to 75; wherein the polymerization processing aid comprises 50 to 95% by weight of methacrylic acid a structural unit of an ester and a structural unit of 5 to 50% by weight of a second monomer, the second monomer being a C ₂ -C ₆ acrylate or a C ₂ -C ₆ methacrylate or a combination thereof; wherein the external lubricant It is a polyol ester or paraffin; and wherein the processing aid has a weight average molecular weight ranging from 5 x 10 ⁵ Daltons to 5 x 10 ⁷ Daltons.

如本文所使用，非定向聚氯乙烯管道係指尚未進行擴張及雙軸定向以形成定向PVC管道之PVC管道。已藉由所屬領域熟知的各種方法中之任一者進行擴張及雙軸定向的非定向PVC管道為定向聚氯乙烯管道(o-PVC管道)。 As used herein, a non-oriented polyvinyl chloride conduit refers to a PVC conduit that has not been expanded and biaxially oriented to form a directional PVC conduit. Non-oriented PVC pipes that have been expanded and biaxially oriented by any of a variety of methods well known in the art are oriented polyvinyl chloride pipes (o-PVC pipes).

加工助劑為甲基丙烯酸甲酯與一或多種單體之共聚物，所述單體選自由C₂-C₆丙烯酸酯及C₂-C₆甲基丙烯酸酯組成之群。如本文所使用，給定單體之術語「結構單元」係指聚合後單體之剩餘物。舉例而言，甲基丙烯酸甲酯之結構單元如圖所示： The processing aid is a copolymer of methyl methacrylate with one or more monomers selected from the group consisting of C ₂ -C ₆ acrylates and C ₂ -C ₆ methacrylates. As used herein, the term "structural unit" of a given monomer refers to the remainder of the monomer after polymerization. For example, the structural unit of methyl methacrylate is shown in the figure:

其中虛線表示結構單元與聚合物主鏈之連接點。 The dotted line indicates the point of attachment of the structural unit to the polymer backbone.

可藉由所屬領域熟知的多種聚合製程中之任一者製備加工助劑。(參見例如美國專利第4,325,856號、第4,654,397號及第4,814,373號。)較佳地，加工助劑包括以下結構單元：a)甲基丙烯酸甲酯及b)一或多種第二單體，其選自由丙烯酸丁酯、甲基丙烯酸丁酯及丙烯酸乙酯組成之群。較佳地，按加工助劑之重量計，加工助劑包括50、更佳60且最佳75重量%至較佳90、更佳85重量%甲基丙烯酸甲酯之結構單元；及較佳10且更佳15重量%至較佳40、更佳30且最佳20重量%一或多種第二單體之結構單元。較佳地，非定向PVC及o-PVC管道中之加工助劑的濃度為每百份PVC 2.5、更佳3.0至5.0重量份。 Processing aids can be prepared by any of a variety of polymerization processes well known in the art. (See, for example, U.S. Patent Nos. 4,325,856, 4,654,397, and 4,814,373.) Preferably, the processing aid comprises the following structural units: a) methyl methacrylate and b) one or more second monomers, A group consisting of butyl acrylate, butyl methacrylate and ethyl acrylate is selected. Preferably, the processing aid comprises, by weight of the processing aid, 50, preferably 60 and most preferably 75% to preferably 90, more preferably 85% by weight of methyl methacrylate structural units; and preferably 10 More preferably, 15% by weight to preferably 40, more preferably 30 and most preferably 20% by weight of one or more structural units of the second monomer. Preferably, the concentration of processing aid in the non-oriented PVC and o-PVC piping is 2.5, preferably 3.0 to 5.0 parts by weight per hundred parts of PVC.

加工助劑之重量平均分子量(M_w)較佳介於1×10⁶道爾頓、更佳2×10⁶道爾頓至較佳4×10⁷道爾頓、更佳2×10⁷道爾頓且最佳1×10⁷範圍內。如本文所使用，加工助劑之M_w係指如ASTM D5296-11中所描述，使用折射率偵測器藉助於使用四氫呋喃及移動相稀釋劑之凝膠滲透層析法(GPC)相對於聚苯乙烯校準標準物所量測之M_w。藉由相同方法測定數目平均分子量(M_n)。 The weight average molecular weight (M _w ) of the processing aid is preferably from 1 × 10 ⁶ Daltons, more preferably from 2 × 10 ⁶ Daltons to preferably from 4 × 10 ⁷ Daltons, more preferably 2 × 10 ⁷ Daiers. It is best in the range of 1 × 10 ⁷ . As used herein, M _{w of} processing aid refers to gel permeation chromatography (GPC) relative to polymerization using a refractive index detector by means of tetrahydrofuran and a mobile phase diluent as described in ASTM D5296-11. M _w measured by the styrene calibration standard. The number average molecular weight (M _n ) was determined by the same method.

外部潤滑劑為多元醇酯或石蠟。較佳多元醇酯之熔點介於52℃至64℃範圍內，包含以Advalube E-2100潤滑劑市售之季戊四醇己二酸硬脂酸酯。石蠟為直鏈或分支鏈C₂₀-C₄₀飽和烴，較佳C₂₀-C₄₀飽和烴或C₂₀-C₄₀飽和烴之混合物，其熔點介於50℃至70℃範圍內。較佳地，外部潤滑劑、較佳石蠟之濃度介於每一百重量份PVC 1.65、更佳1.7至較佳1.9、更佳1.85重量份範圍內。市售石蠟為XL-165石蠟。 The external lubricant is a polyol ester or a paraffin wax. Preferred polyol esters have a melting point in the range of from 52 ° C to 64 ° C and comprise pentaerythritol adipate stearate commercially available as Advalube E-2100 lubricant. Paraffin _₂₀ -C ₂₀ -C mixture of linear or branched C ₂₀ -C ₄₀ saturated hydrocarbons, preferably C ₄₀ C ₄₀ saturated hydrocarbon or saturated hydrocarbon, the melting point ranges from 50 deg.] C to 70 ℃. Preferably, the concentration of the external lubricant, preferably paraffin, is in the range of from 1.65 parts by weight, more preferably from 1.7 to 1.9, more preferably from 1.85 parts by weight per 100 parts by weight of PVC. Commercially available paraffin wax is XL-165 paraffin wax.

如ISO 1628-2：1998中所闡述，K值與PVC之溶液黏度及分子量相關。較佳K值範圍為65至70。 As stated in ISO 1628-2:1998, the K value is related to the solution viscosity and molecular weight of PVC. Preferred K values range from 65 to 70.

非定向PVC管道係藉由多種習知手段中之任一者製備且轉化為o-PVC，包含US 5,203,190、US 4,632,656、 US 5,449,487及US 4,499,045中所描述之彼等手段。藉由AWWA-C909-16測定定向。各種組分之濃度在定向製程過程中不會改變；實際上，伴隨相應的PVC分子定向，管道之內徑通常擴張非定向管道內徑之40%至150%增量。因此，內徑為4"之非定向管道將擴張至5.6"至10"之內徑且無管道強度損失。 Non-oriented PVC pipes are prepared by any of a variety of conventional means and converted to o-PVC, including US 5,203,190, US 4,632,656, They are described in US 5,449,487 and US 4,499,045. Orientation was determined by AWWA-C909-16. The concentration of the various components does not change during the directional process; in practice, the inner diameter of the pipe typically expands from 40% to 150% of the inner diameter of the non-oriented pipe with the corresponding orientation of the PVC molecules. Therefore, a non-oriented pipe with an inner diameter of 4" will expand to an inner diameter of 5.6" to 10" without loss of pipe strength.

有利地，非定向PVC及o-PVC管道包括其他添加劑，每100重量份PVC包含：較佳0.5至2重量份熱穩定劑，諸如甲基或丁基反向酯硫醇錫，市售為Advastab TM-694熱量穩定劑；較佳0.2至3重量份顏料，諸如TiO₂；較佳1至10重量份填充劑，諸如碳酸鈣；較佳0.1至0.5重量份聚乙烯金屬脫模劑，諸如低密度氧化低分子量聚乙烯均聚物，其密度為0.93g/cm³，梅特勒滴點(Mettler drop point)為101℃，且酸值為15，市售為AC-629 LDOxPE潤滑劑；及較佳0.4至2重量份輔助潤滑劑，諸如硬脂酸鈣。 Advantageously, the non-oriented PVC and o-PVC pipes comprise other additives, preferably comprising from 0.5 to 2 parts by weight of heat stabilizer, such as methyl or butyl reverse ester thiolate tin, per 100 parts by weight of PVC, commercially available as Advastab TM-694 heat stabilizer; preferably 0.2 to 3 parts by weight of a pigment such as TiO ₂ ; preferably 1 to 10 parts by weight of a filler such as calcium carbonate; preferably 0.1 to 0.5 part by weight of a polyethylene metal release agent such as low a density oxidized low molecular weight polyethylene homopolymer having a density of 0.93 g/cm ³ , a Mettler drop point of 101 ° C, and an acid number of 15, commercially available as an AC-629 LDOxPE lubricant; Preferably, 0.4 to 2 parts by weight of an auxiliary lubricant such as calcium stearate is used.

在用於製備本發明之非定向及o-PVC管道的特定製程之一實例中，以連續方式將以下各者添加至高強度摻合器中且藉由高強度摻合器摻合：a)PVC；b)熱穩定劑；c)聚乙烯金屬脫模劑；d)輔助潤滑劑；e)顏料；f)填充劑；g)熔點介於60℃至70℃範圍內之石蠟；及h)高分子量丙烯酸加工助劑。隨後藉由漏斗將所得摻合物饋入雙螺桿反轉擠壓機中，所述擠壓機裝配有置於其機筒外部之加熱器區域且具有螺桿調溫能力。擠壓機裝配有具有懸置魚雷心軸之管道頂部模具(圓形輪廓)以在熔融塑膠受到加工且離開模具時獲得管道型材。擠壓機中之加工溫度通常介於205℃至121℃範圍內。通常將由模具及將其連接至擠壓機的接合器構成之工具加熱至150℃至235℃。在管道型材(非定向PVC管道，亦稱為PVC坯料)中之連續熔融流離開模具後，對其進行真空校準且在槽中進行水冷卻以幫助保持其形狀。接著將管道傳送通過設為約100℃之水槽以將管道限制於所述溫度，隨後在固定或不同尺寸之心軸上施力以沿徑向拉伸管道來使PVC分子定向，進而形成o-PVC管道。藉由履帶型拉拔器使連續製程進一步向下游傳送，所述拉拔器將其引導至使其切割為定長之鋸子。或者，可藉由加熱單獨製得之PVC坯料且將其推送通過固持心軸之裝置以沿徑向拉伸管道來產生管道。 In one example of a particular process for making the non-oriented and o-PVC pipes of the present invention, the following are added to the high strength blender in a continuous manner and blended by a high strength blender: a) PVC ; b) heat stabilizer; c) polyethylene metal mold release agent; d) auxiliary lubricant; e) pigment; f) filler; g) paraffin wax having a melting point between 60 ° C and 70 ° C; and h) high A molecular weight acrylic processing aid. The resulting blend was then fed through a funnel into a twin screw reversing extruder equipped with a heater zone placed outside of its barrel and having screw tempering capability. The extruder is equipped with a pipe top mold (circular profile) with a suspended torpedo mandrel to obtain a pipe profile as the molten plastic is processed and exits the mold. The processing temperature in the extruder is usually between 205 ° C and 121 ° C. Inside. The tool consisting of the mold and the adapter that connects it to the extruder is typically heated to 150 ° C to 235 ° C. After the continuous melt stream in the pipe profile (non-oriented PVC pipe, also known as PVC billet) exits the mold, it is vacuum calibrated and water cooled in the tank to help maintain its shape. The pipe is then conveyed through a sink set at about 100 ° C to limit the pipe to the temperature, and then a force is applied to a fixed or different sized mandrel to stretch the pipe radially to orient the PVC molecules to form o- PVC pipe. The continuous process is further conveyed downstream by a track type puller that guides it to a saw that is cut to a fixed length. Alternatively, the conduit can be created by heating a separately formed PVC blank and pushing it through a means for holding the mandrel to stretch the conduit radially.

已出人意料地發現，相比於先前認為之可能量，可將明顯較高量之石蠟潤滑劑以及較高量之高分子量加工助劑添加至PVC調配物中且不對o-PVC管道之最終特性產生有害影響。實際上，國家衛生基金會(National Sanitation Foundation)禁止以處於或低於每100份PVC 1.5重量份之濃度使用石蠟潤滑劑，因為已知此等較高量會降低管道之衝擊強度；此外，所述石蠟潤滑劑之高濃度使潤滑劑堆積於模具上，導致管道脫裂。明顯地，加工助劑之濃度較高對應於PVC管道之定向速率顯著較高；石蠟之濃度較高對應於當使用較高分子量加工助劑時擠出操作速率較高。 Surprisingly, it has been found that a significantly higher amount of paraffin lubricant and a higher amount of high molecular weight processing aid can be added to the PVC formulation than previously thought possible and does not result in the final properties of the o-PVC pipe. Harmful effects. In fact, the National Sanitation Foundation prohibits the use of paraffinic lubricants at concentrations of 1.5 parts by weight or less per 100 parts of PVC, as these higher amounts are known to reduce the impact strength of the pipe; The high concentration of the paraffin lubricant causes the lubricant to build up on the mold, causing the pipe to crack. Obviously, a higher concentration of processing aid corresponds to a significantly higher rate of orientation of the PVC pipe; a higher concentration of paraffin corresponds to a higher rate of extrusion operation when higher molecular weight processing aids are used.

實例 Instance

在下表中，PA-1係指加工助劑，其為甲基丙烯酸甲酯(82重量%)與丙烯酸丁酯(18重量%)之共聚物且具有6.14×10⁶道爾頓之M_w及4.0×10⁴道爾頓之M_n。PA-2係指甲基丙烯酸甲酯(84重量%)、丙烯酸丁酯(12重量%)及甲基丙烯酸丁酯(4重量%)之共聚物且具有2.45×10⁶道爾頓之M_w及6.0×10⁴道爾頓之M_n。加工助劑以含水分散液形式製備，但移除水以形成粉末，所述粉末與PVC、石蠟及其他添加劑組合。PA-b係指甲基丙烯酸甲酯(82重量%)、丙烯酸丁酯(9重量%)及甲基丙烯酸丁酯(9重量%)之共聚物且具有1.4×10⁶道爾頓之M_w及1.4×10⁵道爾頓之M_n。 In the following table, PA-1 refers to a processing aid which is a copolymer of methyl methacrylate (82% by weight) and butyl acrylate (18% by weight) and has a M _{w of} 6.14×10 ⁶ Daltons and 4.0 × 10 ⁴ Daltons of M _n . PA-2 means a copolymer of methyl methacrylate (84% by weight), butyl acrylate (12% by weight) and butyl methacrylate (4% by weight) and has a M _{w of} 2.45 × 10 ⁶ Daltons. and 6.0 × 10 ⁴ daltons M _n. The processing aid is prepared as an aqueous dispersion, but the water is removed to form a powder which is combined with PVC, paraffin and other additives. PA-b means a copolymer of methyl methacrylate (82% by weight), butyl acrylate (9% by weight) and butyl methacrylate (9% by weight) and has a M _{w of} 1.4 × 10 ⁶ Daltons. and 1.4 × 10 ⁵ daltons M _n.

根據ASTM D5296-11(2011)在具有兩個20μm MIXED-A管柱及Wyatt T-rEX折射率偵測器之Agilent 1100系列高壓液相層析儀(「HPLC」)上使用四氫呋喃作為移動相及稀釋劑在0.2mL/min及室溫下測定PA-1、PA-2及PA-b之M_w及M_n。以小於或等於0.3mg/mL之濃度在THF中製備GPC樣品。在無劇烈振盪之情況下於室溫下溶解GPC樣品。在完全溶解後，在分析之前使用WhatmanTM 1-μm PTFE過濾器過濾GPC樣品溶液。 Tetrahydrofuran was used as the mobile phase on an Agilent 1100 Series High Pressure Liquid Chromatograph ("HPLC") with two 20 μm MIXED-A columns and a Wyatt T-rEX refractive index detector according to ASTM D5296-11 (2011) PA-1, PA-2 and PA-b M _n and M _w of the diluent was measured at 0.2mL / min and at room temperature. GPC samples were prepared in THF at concentrations less than or equal to 0.3 mg/mL. GPC samples were dissolved at room temperature without vigorous shaking. After complete dissolution, the GPC sample solution was filtered using a WhatmanTM 1-μm PTFE filter prior to analysis.

表1顯示基準PVC調配物與本發明之調配物之間由PVC調配物製成之棒(模擬未定向管道)的扭矩、進入模具前的熔融壓力(熔融壓力)及表面光滑度的比較。PVC K66係指K值為66之PVC樹脂；TM-694係指Advastab TM-694熱穩定劑；且AC-629係指AC-629 LDOxPE潤滑劑。所有量均按每100份PVC K66之重量份計(phr)。 Table 1 shows the comparison between the torque of the PVC formulation prepared by the PVC formulation (simulated unoriented pipe) between the reference PVC formulation and the formulation of the present invention, the melt pressure (melting pressure) before entering the mold, and the surface smoothness. PVC K66 refers to PVC resin with a K value of 66; TM-694 refers to Advastab TM-694 heat stabilizer; and AC-629 refers to AC-629 LDOxPE lubricant. All amounts are in parts per hundred parts by weight of PVC K66 (phr).

結果顯示，相比於所認為可能的操作速率，以明顯較高之石蠟潤滑劑操作速率達成類似扭矩、熔融壓力及o-PVC表面光滑度。 The results show that similar torque, melt pressure and o-PVC surface smoothness are achieved at significantly higher paraffin lubricant operating rates than would be expected.

Claims

一種非定向聚氯乙烯管道，按所述管道之重量計，其包括：a)聚氯乙烯；b)每100重量份所述聚氯乙烯2至5重量份聚合加工助劑；及c)每100重量份所述聚氯乙烯1.6至2.0重量份外部潤滑劑；其中所述聚氯乙烯之K值介於60至75範圍內；其中所述聚合加工助劑包括50至95重量%甲基丙烯酸甲酯之結構單元及5至50重量%第二單體之結構單元，所述第二單體為C₂-C₆丙烯酸酯或C₂-C₆甲基丙烯酸酯或其組合；其中所述外部潤滑劑為多元醇酯或石蠟；且其中所述加工助劑之重量平均分子量介於5×10⁵道爾頓至5×10⁷道爾頓範圍內。 A non-oriented polyvinyl chloride pipe comprising, based on the weight of the pipe, a) polyvinyl chloride; b) 2 to 5 parts by weight of a polymerization processing aid per 100 parts by weight of the polyvinyl chloride; and c) 100 parts by weight of the polyvinyl chloride 1.6 to 2.0 parts by weight of an external lubricant; wherein the polyvinyl chloride has a K value in the range of 60 to 75; wherein the polymerization processing aid comprises 50 to 95% by weight of methacrylic acid a structural unit of a methyl ester and a structural unit of 5 to 50% by weight of a second monomer, the second monomer being a C ₂ -C ₆ acrylate or a C ₂ -C ₆ methacrylate or a combination thereof; The external lubricant is a polyol ester or paraffin wax; and wherein the processing aid has a weight average molecular weight ranging from 5 x 10 ⁵ Daltons to 5 x 10 ⁷ Daltons.

如申請專利範圍第1項所述的非定向管道，其中所述加工助劑包括60至90重量%甲基丙烯酸甲酯及10至40重量%所述第二單體，所述第二單體為丙烯酸丁酯、甲基丙烯酸丁酯、或丙烯酸乙酯或其組合；其中所述加工助劑之重量平均分子量介於1×10⁶道爾頓至2×10⁷道爾頓範圍內；且其中所述非定向聚氯乙烯管道中之所述加工助劑的濃度為每100重量份所述聚氯乙烯2.5至5.0重量份。 The non-oriented pipe according to claim 1, wherein the processing aid comprises 60 to 90% by weight of methyl methacrylate and 10 to 40% by weight of the second monomer, the second monomer Is butyl acrylate, butyl methacrylate, or ethyl acrylate or a combination thereof; wherein the processing aid has a weight average molecular weight ranging from 1×10 ⁶ Daltons to 2×10 ⁷ Daltons; Wherein the concentration of the processing aid in the non-oriented polyvinyl chloride piping is from 2.5 to 5.0 parts by weight per 100 parts by weight of the polyvinyl chloride.

如申請專利範圍第1項或第2項中任一項所述的非定向管道，其中所述外部潤滑劑為石蠟，其濃度介於每100重量份所述聚氯乙烯1.65至1.9重量份範圍內。 The non-oriented pipe according to any one of the preceding claims, wherein the external lubricant is paraffin, and the concentration thereof is in the range of 1.65 to 1.9 parts by weight per 100 parts by weight of the polyvinyl chloride. Inside.

如申請專利範圍第3項所述的非定向管道，其中所述非定向聚氯乙烯管道之K值為65至70；且其中所述石蠟之熔點介於60℃至80℃範圍內。 The non-oriented pipe according to claim 3, wherein the non-oriented polyvinyl chloride pipe has a K value of 65 to 70; and wherein the paraffin has a melting point of from 60 ° C to 80 ° C.

如申請專利範圍第1項至第4項中任一項所述的非定向管道，其額外包括0.5至2份熱穩定劑；0.2至3份顏料；1至10份填充劑；0.1至0.5份聚乙烯金屬脫模劑；及0.4至2份硬脂酸鈣。 The non-oriented pipe according to any one of claims 1 to 4, which additionally comprises 0.5 to 2 parts of heat stabilizer; 0.2 to 3 parts of pigment; 1 to 10 parts of filler; 0.1 to 0.5 parts a polyethylene metal release agent; and 0.4 to 2 parts of calcium stearate.

如申請專利範圍第5項所述的非定向管道，其中所述熱穩定劑為甲基或丁基反向酯硫醇錫；所述顏料為TiO₂；所述填充劑為碳酸鈣；且所述聚乙烯金屬脫模劑為低密度氧化低分子量聚乙烯均聚物，其密度為0.93g/cm³，梅特勒滴點(Mettler drop point)為101℃且酸值為15。 The non-oriented pipe according to claim 5, wherein the heat stabilizer is methyl or butyl reverse ester thiol tin; the pigment is TiO ₂ ; the filler is calcium carbonate; The polyethylene metal release agent is a low density oxidized low molecular weight polyethylene homopolymer having a density of 0.93 g/cm ³ , a Mettler drop point of 101 ° C and an acid value of 15.

一種定向聚氯乙烯管道，按所述管道之重量計，其包括：a)定向聚氯乙烯；b)每100重量份所述聚氯乙烯2至5重量份聚合加工助劑；及c)每100重量份所述聚氯乙烯1.6至2.0重量份外部潤滑劑；其中所述聚氯乙烯之K值介於60至75範圍內；其中所述聚合加工助劑包括50至95重量%甲基丙烯酸甲酯之結構單元及5至50重量%第二單體之結構單元，所述第二單體為C₂-C₆丙烯酸酯或C₂-C₆甲基丙烯酸酯或其組合；且其中所述加工助劑之重量平均分子量介於5×10⁵道爾頓至5×10⁷道爾頓範圍內。 An oriented polyvinyl chloride pipe comprising, based on the weight of the pipe, a) oriented polyvinyl chloride; b) 2 to 5 parts by weight of a polymerization processing aid per 100 parts by weight of the polyvinyl chloride; and c) 100 parts by weight of the polyvinyl chloride 1.6 to 2.0 parts by weight of an external lubricant; wherein the polyvinyl chloride has a K value in the range of 60 to 75; wherein the polymerization processing aid comprises 50 to 95% by weight of methacrylic acid a structural unit of a methyl ester and a structural unit of 5 to 50% by weight of a second monomer, the second monomer being a C ₂ -C ₆ acrylate or a C ₂ -C ₆ methacrylate or a combination thereof; The processing aid has a weight average molecular weight ranging from 5 x 10 ⁵ Daltons to 5 x 10 ⁷ Daltons.