CN102642288A - 生产棒的方法 - Google Patents
生产棒的方法 Download PDFInfo
- Publication number
- CN102642288A CN102642288A CN2012100349282A CN201210034928A CN102642288A CN 102642288 A CN102642288 A CN 102642288A CN 2012100349282 A CN2012100349282 A CN 2012100349282A CN 201210034928 A CN201210034928 A CN 201210034928A CN 102642288 A CN102642288 A CN 102642288A
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- CN
- China
- Prior art keywords
- plastic
- rod
- aforementioned arbitrary
- shaping material
- diameter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
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- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical class C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/60—Measuring, controlling or regulating
- B29C44/605—Calibration following a shaping operation, e.g. extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/84—Fasteners therefor or fasteners being internal fixation devices
- A61B17/86—Pins or screws or threaded wires; nuts therefor
- A61B17/866—Material or manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
- B29C44/32—Incorporating or moulding on preformed parts, e.g. linings, inserts or reinforcements
- B29C44/322—Incorporating or moulding on preformed parts, e.g. linings, inserts or reinforcements the preformed parts being elongated inserts, e.g. cables
- B29C44/324—Incorporating or moulding on preformed parts, e.g. linings, inserts or reinforcements the preformed parts being elongated inserts, e.g. cables the preformed parts being tubular or folded to a tubular shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/06—Rod-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/298—Feeding the extrusion material to the extruder in a location other than through a barrel, e.g. through a screw
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2002/30001—Additional features of subject-matter classified in A61F2/28, A61F2/30 and subgroups thereof
- A61F2002/30003—Material related properties of the prosthesis or of a coating on the prosthesis
- A61F2002/30004—Material related properties of the prosthesis or of a coating on the prosthesis the prosthesis being made from materials having different values of a given property at different locations within the same prosthesis
- A61F2002/30011—Material related properties of the prosthesis or of a coating on the prosthesis the prosthesis being made from materials having different values of a given property at different locations within the same prosthesis differing in porosity
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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Abstract
一种生产棒的方法,其包括:a)由第一塑料成型物料挤出塑料型材,该第一塑料成型物料形成了最外面的层,并且其的至少50重量%由部分结晶热塑性塑料组成,b)在校准器内,将第二塑料成型物料填入到新挤出的型材中,和c)校准,抽出和冷却该新形成的棒,其中该第一塑料成型物料具有下面的参数:-根据ISO11357的晶粒熔点Tm是至少170℃,-根据ISO11357的结晶温度Tk比Tm低最多70K,和-根据ISO11357的熔融焓ΔH是至少20J/g,该方法能够生产在直径和直线性方面具有高尺寸精度的棒,特别是圆棒。该棒特别适于作为半成品,来通过切削生产成品件。
Description
技术领域
本发明涉及一种挤出由部分结晶热塑性塑料制成的棒的方法。该棒可以是致密的;它们在此情况下被称作实心棒。在这里一种具体的情况是圆棒。根据EN ISO15860,圆棒是挤出的,浇注的或者压塑成的长形的,直的,实心产品,具有在它们的整个长度上保持相同的圆形横截面。
背景技术
由热塑性塑料制成的棒优选用于切削生产成品件,特别是具有相对小生产件数的成品件,原型件或者注塑方法或者其他塑料加工仅仅难以生产或者几乎不能生产的零件。
从用户的观点来说,由高熔点热塑性塑料例如聚醚醚酮(PEEK)所生产的这种类型的部件更类似于传统的金属加工:标准化的半成品例如管,型材或者棒被以希望的形状切削加工到一定程度。传统的塑料制造方法仅仅用于生产半成品:型材,管或者实心棒因此原则上是在挤出机中以这样的方式来挤出的,其与由PP或者PE制成的相应的半成品的生产过程中所用的常见方式相同。
具有相对小直径的棒可以通过常规的热塑性塑料成型物料挤出来获得良好的品质。但是,这种方法对于从大约20mm直径起的棒来说变得困难,这取决于所用的成型物料,因为由于经由冷却从该挤出棒中排出的大量热能,只有在长的冷却时间之后才能达到足够的尺寸稳定性,这具有不利的作用,即,该棒的自重会引起它下垂,会导致形成横截面变化,或者会发生挠曲。如果降低挤出速率来产生用于所述棒的更好的冷却条件,则制造成本会增加到经济上不可接受的值。
申请DE102004015072 A1声称在挤出方法过程中将塑料熔体在模具中分成两个流,其中由布置在外侧的熔体依照常规方法挤出管。该第二熔体是通过喷枪填入到所述管中的。为了防止所述管坍塌,通过所述头引入支承空气,并且在校准系统中施加减压。已经显示这种方法能够制造圆棒,其具有优异的光学性能和特别是高的横截面尺寸精度。
申请DE3718036 A1描述了一种通过多层挤出来生产具有大的横截面尺寸的成型件的方法,例如由聚乙烯制成的减振器或者保护性覆层。在这里将第一熔融材料流用于模制中空型材,其在校准器包套中冷却,同时将第二熔融材料流挤入到所述空腔中。这里将熔体大致注射到型材离开校准系统的位置。外部的中空型材(其已经凝固,但是其仍然具有一定程度的柔韧性)在这种方法过程中膨胀成凸面形状,因此接受了比实际期望更多体积的一些材料。随后在冷却过程中的收缩抑制了空腔或者空泡的形成。
但是,该现有技术是不令人满意的。申请DE102004015072 A1仅仅涉及非晶态热塑性塑料。如果尝试以这种方式来加工部分结晶热塑性塑料,则这些材料相对高的收缩会使得冷却过程中存在形成空腔的危险,它们对于进一步的加工来说是不可接受的。DE3718036 A1的尝试(其通过使用有针对性的膨胀来对抗空腔的形成)在精确的尺寸精度是重要的情况中是不可行的。
发明内容
本发明的目标在于生产由部分结晶热塑性塑料生产棒,其满足下面的要求:
-在从大约20mm直径起的棒直径尺寸精度方面,应当实现优于常规的挤出。在理想的情况中,应当非常充分地实现或者低于标准DIN16980和EN ISO15860所规定的容限;
-所述棒相对于直轴线的偏离,基于它的外边缘和1米的长度,同样应当尽可能小。相对于直线性的偏离会在切削制造过程中引起问题;
-实心棒应当无空腔或者空泡,因为它们将是进一步加工过程中的大问题,并且对于随后成品件的功能也是大问题;
-实心棒此外应当具有尽可能低的内应力水平,来促进切削加工和降低由于加工会产生的翘曲。内应力水平可以从由该实心棒上仔细切割下的薄板的翘曲来评价;
-最后,应当可以生产多层棒,在其中所述层由不同的材料组成。
这个目标是通过生产棒的方法来实现的,其中:
a)由第一塑料成型物料挤出塑料型材,该第一塑料成型物料形成了最外面的层,且其至少50重量%,优选至少60重量%,特别优选至少70重量%和特别优选至少80重量%由部分结晶热塑性塑料构成,
b)在校准器内,用第二塑料成型物料填充新挤出的型材,和
c)校准,抽出和冷却该新形成的棒,
特征在于该第一塑料成型物料具有下面的参数:
-晶粒熔点 Tm是至少170℃,优选至少185℃,特别优选至少200℃和特别优选至少215℃,
-结晶温度 Tk比Tm 低最多70K,优选比Tm 低最多60K,特别优选比Tm 低最多55 K和特别优选比Tm 低最多50K,和
-熔融焓ΔH是至少20J/g,优选至少25 J/g,特别优选至少30J/g,特别优选至少35 J/g和非常特别优选至少40J/g,作为结晶度的量度,
这里Tm,Tk和ΔH是根据ISO11357,如下来确定的:从室温以20K/min的加热速率加热到最大390℃,以20K/min的加热速率冷却到-60℃,和以20K/min的加热速率重新加热到最大390℃。Tm和ΔH是在第2加热程序中确定的,而Tk是在冷却程序中确定的。最大加热温度取决于热稳定性,以及还取决于Tm;在这里建议超过Tm至少大约60K。
该第一塑料成型物料的晶粒熔点 Tm必须是至少170℃,目的是确保挤出型材足够快的凝固。但是,这种条件本身不是足够的。如果结晶延迟,则离开校准系统之后型材的柔韧性将仍然足以引起扩大(Aufweitung),其是由于填料的物料压力而形成的。为此原因,还必需使得冷却过程中的结晶尽可能快地开始,即,使得Tk尽可能大。结晶度此外必须足够高来确保期望的凝固。这会在经验上与熔融焓相关。
根据本发明所生产的棒可以是圆棒;但是,其他几何形状也是可能的,横截面的例子是卵形,椭圆形或者多边形(例如三角形,正方形,矩形,菱形,梯形,五边形或者六边形)。在圆棒的情况中,步骤a)中挤出的型材是管。该型材可以具有一个层,并因此仅仅由该第一塑料成型物料组成,或者具有多层,这里至少最外面的层由该第一塑料成型物料组成。
该第一塑料成型物料基于部分结晶热塑性塑料,其作为例子可以是聚酰胺,部分芳族聚酯,含氟聚合物(例如 PFA,ETFE,EFEP,PVDF,PTFE),聚苯硫醚或者聚亚芳基醚酮。在该热塑性塑料选择过程中需要考虑的尤其是结晶温度Tk和熔融焓会受到该成型物料其他成分的影响。Tk可以例如通过加入成核剂来明显提高。
聚酰胺可以由二胺和二羧酸的组合,由ω-氨基羧酸或者由相应的内酰胺来生产。原则上,可以使用任何足够部分结晶的聚酰胺,例如PA6,PA66或者共聚酰胺,其使用这种基物,具有来自于对苯二甲酸和/或间苯二甲酸的单元(通常成为PPA),或者PA9T和PA10T和它们与其他聚酰胺的共混物。其他合适的聚酰胺的例子是PA610,PA88,PA8,PA612,PA810,PA108,PA9,PA613,PA614,PA812,PA128,PA1010,PA10,PA814,PA148,PA1012,PA11,PA1014,PA1212和PA12。当然也可以使用基于其的共聚酰胺。该聚酰胺的生产是现有技术。
同样可以使用不同的聚酰胺的混合物,前提为相容性是足够的。可相容的聚酰胺组合是本领域技术人员已知的;在此可以提及的例子是下面组合:PA12/PA1012,PA12/PA1212,PA612/PA12,PA613/PA12,PA1014/PA12和PA610/PA12,以及含PA11的相应组合。在有疑义的情况中,可相容的组合可以通过常规试验来确定。
热塑性聚酯是通过二醇与二羧酸或者与其的聚酯形成性衍生物的缩聚来生产,衍生物的例子是二甲基酯。合适的二醇具有式HO-R-OH,这里R是二价的支化或者未支化的脂肪族和/或环脂族残基,其具有2-18,优选2-12个碳原子。合适的二羧酸具有式HOOC-R'-COOH,这里 R'是二价芳族残基,具有6-20,优选6-12个碳原子。
可以提及的二醇的例子是乙二醇,三亚甲基二醇,四亚甲基二醇,2-丁烯-1,4-二醇,六亚甲基二醇,新戊二醇以及环己烷二甲醇。该二醇可以单独使用或者作为二醇混合物来使用。
芳族二羧酸的例子包括对苯二甲酸,间苯二甲酸,1,4-,1,5-,2,6-或者2,7-萘二羧酸,联苯基-4,4'-二羧酸和二苯基醚4,4'-二羧酸。至多30mol%的这些二羧酸可以用具有3-50个碳原子和优选具有6-40个碳原子的脂肪族或者环脂族二羧酸替代,例如琥珀酸,己二酸,癸二酸,十二双酸(Dodecandis?ure)或者环己烷-1,4-二羧酸。
合适的聚酯的例子是聚对苯二甲酸丙二醇酯,聚对苯二甲酸丁二醇酯,聚2,6-萘二甲酸乙二醇酯,聚2,6-萘二甲酸丙二醇酯和聚2,6-萘二甲酸丁二醇酯。
这些聚酯的生产是现有技术(DE-OSS 2407155,2407156;Ullmann's Enzyklop?die der technischen Chemie [乌尔曼化工百科全书],第4版第19卷从第65页起,Verlag Chemie,Weinheim,1980)。
含氟聚合物作为举例可以是聚1,1-偏二氟乙烯(PVDF),乙烯-四氟乙烯共聚物(ETFE),用第三成分例如丙烯,六氟丙烯,氟乙烯或者1,1-偏二氟乙烯改性的ETFE(例子是EFEP)或者四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)。
聚苯硫醚包含下式的单元:(-C6H4-S-);
它的至少50重量%,至少70重量%或者至少90重量%由这些单元构成。其余单元可以是下面在聚亚芳基醚酮情况给出的那些,或者三-或者四官能的支化剂单元,其来自于例如合成过程中伴随使用的三氯苯或者四氯苯。
聚苯硫醚以广泛多种类型或者成型物料形式市售。
聚亚芳基醚酮包含下式的单元:(-Ar-X-)和(-Ar'-Y),这里Ar和Ar’是二价芳族残基,优选1,4-亚苯基,4,4’-亚联苯基,或者1,4-,1,5-或者2,6-亚萘基。X是吸电子基团,优选羰基或者硫酰基,而Y是另外的基团例如 O,S,CH2,异亚丙基等。这里至少50%,优选至少70%和特别优选至少80%的基团X是羰基,而至少50%,优选至少70%和特别优选至少80%的基团Y由氧构成。
在优选的实施方案中,100%的基团X由羰基构成和100%的基团Y由氧构成。在所述的实施方案中,该聚亚芳基醚酮作为举例可以是聚醚醚酮(PEEK;式I),聚醚酮(PEK;式II),聚醚酮酮(PEKK;式III)或者聚醚醚酮酮(PEEKK;式IV),但是羰基和氧基团的其他排列自然也是可能的。
该聚亚芳基醚酮是部分结晶的,这作为举例,在DSC分析中通过晶粒熔点 Tm的出现来辨别,其在大部分情况中是是300℃或者更高量级的。
该成型物料可以包含另外的成分例如冲击改性剂,其他热塑性塑料,增塑剂和其他常规添加剂,例如颜料或者填料,例如炭黑,二氧化钛,硫化锌,增强纤维例如玻璃纤维或者碳纤维,或者晶须,润滑剂,例如石墨,二硫化钼,氮化硼或者PTFE,成核剂,例如滑石粉,加工助剂,例如蜡,硬脂酸锌或者硬脂酸钙,抗氧化剂,UV稳定剂,以及赋予产品抗静电性能的添加剂,例如碳纤维,石墨原纤,不锈钢纤维,或者导电炭黑。
在第一实施方案中,该第一和第二成型物料是相同的。在这种情况中,该熔体流可以有利的分开,如DE102004015072A1中所述。
在第二实施方案中,该第一和第二成型物料是不同的,但是第二成型物料落入与第一成型物料相同的要求保护的定义内。当在两种情况下它们所基于的热塑性塑料相同,但是成型物料的其他成分的类型和/或量不同时,尤其是这种情况。在其他情况中,两种热塑性塑料是不同的,但是是相互相容性的。
在第三实施方案中,第二成型物料不落入与第一成型物料相同的要求保护的定义内。它可以是部分结晶或者非晶态的。可以提及的例子是透明聚酰胺,聚丙烯,聚对苯二甲酸乙二醇酯,聚碳酸酯,全芳族聚酯,聚酯碳酸酯,聚砜,聚醚砜,聚苯砜,聚苯醚,聚醚酰亚胺和聚酰亚胺,或者由聚亚芳基醚酮与任选的相对大比例的聚砜,聚醚砜,聚苯砜,聚醚酰亚胺和/或聚酰亚胺的共混物。该第二成型物料可以包含在用于第一成型物料的在前面所列出的通常的添加剂。为了良好地结合两种材料,在两种成型物料之间必须存在着足够的附着相容性。
在第四实施方案中,步骤a)中挤出的型材已经发泡。该发泡可以通过加入易于分解的发泡剂来化学进行,或者可以计量添加发泡气体来物理进行。膨胀度(定义为泡沫密度与未发泡的成型物料的密度之比)优选是1.01-10。该泡沫可以是开孔的或者闭孔的。该第四实施方案可以与第一,第二或者第三实施方案相结合。
在第五实施方案中,在步骤b)中填入的第二塑料成型物料已经进行了发泡。对于第四实施方案的描述同样适于此处。该第五实施方案可以与第一,第二,第三或者第四实施方案相结合。
对于目标应用来说,令人期望的是在最终的棒中,步骤a)中挤出的型材和步骤b)中填入的芯彼此牢固地粘附在一起。为此目的,两种成型物料必须具有足够的相互相容性。在其中相容性不足的情况中,该型材可以在多个层中共同挤出,这里最里面的层由合适的附着力促进剂构成。在PA12(型材)和PA6(芯)的情况中,相容性作为举例可以通过由PA612制成的附着力促进剂层来提高;而在PA612(型材)和聚对苯二甲酸乙二醇酯(PET;芯)的情况中,相容性作为举例可以通过由PA612/PET共混物(其包含PA612-PET嵌段共聚物)制成的附着力促进剂层来产生。
此外,为了实现良好的附着性,在步骤b)中填入的芯材料熔体的温度水平应当至少处于形成挤出型材内表面的材料的Tm范围内。
挤出机下游的校准器被用于成形所述外层。这里可以使用例如典型的管线挤出中所用的黄铜校准系统(Messing-Kalibrierung)。该校准系统如果期望可以具有强的冷却来提供快速的热耗散或者具有加热,来提供相对慢的冷却和因此降低棒中产生的应力。建议使用校准器的温度控制来调整挤出的塑料型材的温度,来确保第二成型物料的可靠附着。这在型材具有低壁厚时是特别需要考虑的。
该第二塑料成型物料作为熔体在这样的位置引入,其优选处于校准器长度的大约1%-大约99%,特别优选处于大约10%-大约90%,特别优选处于大约20%-大约80%内和非常特别优选处于大约30%-大约70%内。在特殊情况中,具体地,当该挤出的型材具有比较高的壁厚和/或该第一塑料成型物料具有比较高的弹性模量和因此高的刚度时,也可以在校准器之后才引入该第二成型物料,不发生型材的任何扩大。在这些前提下,这种类型的实施方案与本发明的方法是等价的。该第二塑料成型物料的物料压力是2-8bar;允许仅仅非常小的波动,以可靠地生产无空泡的棒。该压力对于生产发泡芯来说可以更小。
在校准器的下游,可以存在着冷却和/或调温区,其中布置有不同的冷却介质或者加热介质。在这里可以使用水浸浴,喷涂浴和/或鼓风。将相对大直径的棒,或者由纤维填充的成型物料制成的实心棒,特别要调节温度或者按一定方法冷却,来避免过多的内应力和避免棒因此过早破坏。
抽出速度通常取决于直径和所用的成型物料。较小的直径是以较高的速度产生的。
本发明的方法可以与柔性校准系统相结合,因此能够无级地(stufenlos)生产不同的棒直径。这种类型的校准系统已经用于管挤出中(例如WO2004/091891,DE102004029498 B3,EP1627724 A2,WO00/16963和WO2005/018910)。使用柔性校准系统具有大的经济利益,因为部件的制造通过将棒以切削加工方法达到了所需的尺寸。特别地,对于由昂贵的成型物料所制成的高价值棒来说,必须从外直径上切削加工的量尽可能少在经济上是重要的。这在实心棒市售中导致例如以大约5mm-大约40mm直径的直径范围内以1mm步长的直径提供,并且生产批次量经常非常小。
在本发明上下文中,可以生产这样的棒,其的直径(或者在其中不以圆形横截面存在的情况中是最小直径)是15-500mm,优选20-400mm和特别优选25-350mm。这里步骤a)中挤出的型材的壁厚通常是直径的0.2-25%,优选是直径的0.4-20%,特别优选是直径的0.6-16%和特别优选是直径的0.8-14%。如果不存在圆形横截面,则“直径”表示最小直径。
在本发明上下文中,多层棒,特别是多层圆棒是特别令人感兴趣的。这里可能的实施方案的例子如下:
-对于例如齿轮、杆或者车轴应用来说,耐磨或者抗磨外层和坚韧的芯是优异的先决条件,例子是外侧为PEEK成型物料,具有30%的碳纤维或者分别具有10%的碳纤维,石墨和PTFE或者具有30%的陶瓷填料,和内侧为未增强的PEEK成型物料。
-在具有纤维填充的芯材料和未填充的外层的实心棒情况下,可以组合高强度材料和光滑表面。
-另外一种可能性在于,选择具有良好切削加工能力的外层,例如由与芯相同的原料,但是具有较低分子量的材料制成的外层。
-为了降低材料成本,实心棒可以由高价值外层(例如 PEEK)和不太昂贵的芯部件构成,例如含PFA,聚酰亚胺,聚醚酰亚胺,LCP例如液晶聚酯,聚砜,聚醚砜,聚苯砜,聚苯并咪唑(PBI)和/或其他耐高温聚合物的PEEK共混物。
-在另外一种实施方案中,棒可以由硬致密外层和发泡芯来生产。这种方法将发泡材料填入到可利用的管空间中;膨胀度和所述泡孔构成(Zelligkeit)可以通过使用所选择的参数,例如熔体刚度,发泡剂量,发泡剂类型等以已知的方式来控制。这种方式能够产生跨整个横截面的均匀的泡孔直径。这里主要的目标是降低重量,例如在航空航天中的轻质结构应用。
-特别是对于医学应用,例如对于植入件,感兴趣还有发泡的外层与硬的或者坚韧的芯的组合。发泡外层改善了血管发生或者骨融合,同时坚固的稳定的芯具有负载功能。开孔泡沫在此是有利的。用于医用的一种可能的实施方案是由权利要求的棒所生产的零件,具有由未填充的PEEK成型物料所制成的致密芯和由开孔发泡的PEEK成型物料制成的外层,后者的泡孔直径的数均值是1μm-700μm,优选10μm-500μm。
-此外可以对预挤出的管和芯二者发泡,例如在期望不同的泡沫结构时。在植入件的情况中,当需要或者可以实现不同程度的骨融合时,可以以此方式生产具有不同泡孔结构的植入件,例如由PEEK成型物料制成的植入件,来产生有针对性的融合。
本发明还提供了根据本发明由一种或多种PEEK成型物料所制造的棒的用途,其用于生产植入件。
足够的尺寸稳定性可以在挤出的型材中用本发明的方法,比现有技术更快地实现。该第二成型物料的填入因此可以在距离校准系统末端一定距离处发生,以使得芯材料在物料压力下具有足够长的凝固时间,而没有型材的任何扩大。这有效地抑制了空泡的形成。这样所形成的棒的尺寸精度优于现有技术所生产的棒。
具体实施方式
实施例
下面的成型物料用于实施例和对比例中:
PA12:VESTAMID? LX9030,黄色,具有下面的参数:Tm=176℃,Tk=149℃和ΔH=64 J/g,在每种情况中通过DSC方法根据ISO11357来测量;
PEEK:VESTAKEEP?4000G nf,具有下面的参数:Tm=336℃,Tk=281℃和ΔH=42 J/g,在每种情况中通过DSC方法根据ISO11357来测量。
对比例1:
直径65mm的实心棒是通过标准挤出方法,由PA12来挤出的。表1给出了试验条件和结果。
实施例1:
直径65mm的实心棒是通过使用双层模具由PA12来挤出的;外层厚度5mm;喷枪在校准器长度的70%处终止。参见表1。
对比例2:
直径65mm的实心棒是通过标准挤出方法,由PEEK来挤出的;参见表2。
实施例2:
直径65mm的实心棒是通过使用双层模具方法由PEEK来挤出的;外层厚度5mm;喷枪在校准器长度的70%处终止。参见表2。
Claims (14)
1.生产棒的方法,其中:
a)由第一塑料成型物料挤出塑料型材,该第一塑料成型物料形成了最外面的层并且其至少50重量%由部分结晶热塑性塑料构成,
b)在校准器内,用第二塑料成型物料填充新挤出的型材,和
c)校准,抽出和冷却该新形成的棒,
特征在于该第一塑料成型物料具有下面的参数:
-根据ISO11357的晶粒熔点 Tm是至少170℃,
-根据ISO11357的结晶温度 Tk比Tm低最多70K,和
-根据ISO11357的熔融焓ΔH是至少20J/g。
2.根据权利要求1的方法,特征在于该棒是圆棒。
3.根据前述任一权利要求的方法,特征在于该第一塑料成型物料的热塑性塑料选自:聚酰胺,部分芳族聚酯,含氟聚合物,聚苯硫醚和聚亚芳基醚酮。
4.根据前述任一权利要求的方法,特征在于该第二塑料成型物料的热塑性塑料选自:聚酰胺,部分芳族聚酯,含氟聚合物,聚苯硫醚,聚亚芳基醚酮,透明的聚酰胺,聚丙烯,聚对苯二甲酸乙二醇酯,聚碳酸酯,全芳族聚酯,聚酯碳酸酯,聚砜,聚醚砜,聚苯砜,聚苯醚,聚醚酰亚胺,聚酰亚胺,和由聚亚芳基醚酮与聚砜,聚醚砜,聚苯砜,聚醚酰亚胺和/或聚酰亚胺得到的共混物。
5.根据前述任一权利要求的方法,特征在于该第一和第二塑料成型物料是相同的。
6.根据前述任一权利要求的方法,特征在于在步骤a)中挤出的该塑料型材已经进行了发泡。
7.根据前述任一权利要求的方法,特征在于在步骤b)中填入的该第二塑料成型物料已经进行了发泡。
8.根据前述任一权利要求的方法,特征在于在步骤a)中挤出的该塑料型材是多层的,其中最里面的层由附着力促进剂构成。
9.根据前述任一权利要求的方法,特征在于所述棒的直径或者最小直径是15-500mm。
10.根据前述任一权利要求的方法,特征在于在步骤a)中挤出的该塑料型材的壁厚是所述直径或者最小直径的0.4-20%。
11.根据前述任一权利要求所生产的棒用于通过切削加工来生产成品件的用途。
12.根据权利要求11的用途,特征在于该棒由一种或多种聚醚醚酮成型物料构成,和该成品件是植入件。
13.根据权利要求12所获得的植入件。
14.根据权利要求13的植入件,特征在于它包含未发泡的芯和其中数均泡孔直径是1-700μm的开孔发泡的外层。
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- 2011-02-17 DE DE102011004305A patent/DE102011004305A1/de not_active Withdrawn
-
2012
- 2012-01-30 EP EP12153040.6A patent/EP2489494B1/de not_active Not-in-force
- 2012-02-15 US US13/396,643 patent/US20120232531A1/en not_active Abandoned
- 2012-02-15 BR BRBR102012003478-6A patent/BR102012003478A2/pt not_active Application Discontinuation
- 2012-02-16 KR KR1020120015632A patent/KR20120102506A/ko active IP Right Grant
- 2012-02-16 RU RU2012105418/04A patent/RU2598851C2/ru not_active IP Right Cessation
- 2012-02-16 CN CN2012100349282A patent/CN102642288A/zh active Pending
- 2012-02-17 JP JP2012033319A patent/JP6234006B2/ja not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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DE102011004305A1 (de) | 2012-08-23 |
RU2598851C2 (ru) | 2016-09-27 |
US20120232531A1 (en) | 2012-09-13 |
EP2489494A1 (de) | 2012-08-22 |
BR102012003478A2 (pt) | 2014-02-11 |
JP6234006B2 (ja) | 2017-11-22 |
JP2012171357A (ja) | 2012-09-10 |
RU2012105418A (ru) | 2013-08-27 |
EP2489494B1 (de) | 2017-06-28 |
KR20120102506A (ko) | 2012-09-18 |
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