• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Composite consists of a combination of polyalkyl methacrylate (I) with polyvinylidene fluoride (PVDF) and of (I) with a thermoplastic polymer (II), which is incompatible with PVDF. The composite has >=1 outer surface of PVDF and a surface of (II). PVDF and (II) pref. are joined through (a substance contg.) (I). The composite pref. is produced by coextrusion of (I) or a mixt. contg. >=30 wt. % (I) between PVDF and (II). The composite can be made into tubes, hoses, profiles, films and sheets (suitable for thermoforming). It has a homogeneous structure, in which the components are intimately bonded.
    公开号:SU1071216A3
    申请号:SU792818055
    申请日:1979-09-24
    公开日:1984-01-30
    发明作者:Страссель Альбер
    申请人:Продюи Шимик Южин Кюльманн (Фирма)；
    IPC主号:
    专利说明:


    N0
    The invention relates to plastics-based composite materials, namely, laminates, one or several layers of which are made of polyvinylidene fluoride. A layered material is known that contains a layer of polytetrafluoroethyl and a layer of dyklotkan impregnated with polyvinylideneftbrid (PVDF), on which a layer of polyvinylidene fluoride 1 can be applied. HeiiocTaTKOM of a known laminate is relatively low in the interlayer of adhesion. The closest in technical essence and the achieved result to the proposed is a layered material comprising an upper thermoplastic layer, an intermediate adhesive layer and a lower layer of polyvinylidene fluoride. The upper layer is made of polyethylene or polypropylene, the adhesion layer is made of ethylene-vinyl acetate copolymer, chlorinated polyethylene, thermoplastic polyurethane 2. The lack of such a layered material also consists in low interlayer adhesion. The purpose of the invention is to increase the interlayer adhesion of the layered material. The goal is achieved by the fact that in a layered material comprising a top layer of thermoplastic, an intermediate adhesive layer and a bottom layer of polyvinylidene fluoride, the top layer is made of a thermoplastic selected from the group consisting of an acrylonitrile butadiene-resin and a mixture of a mixture of a layer and a layer of polyvinylidene fluoride. polystyrene, and a layer of polymethyl methacrylate or a mixture containing 40 parts by weight was used as an intermediate adhesive layer. polymethyl methacrylate, 30 wee. a copolymer of acrylonitrile-butadiene styrene and 30 parts by weight; polyvinylidene fluoride, or mixtures containing 30 parts by weight; polymethyl methacrylate, 40 weight.h. acrylic rubber and 30 weight.h. copolymer of acrylonitrile butadiene styrene. The application of the invention allows to obtain a new composite mother. al, having solidity, having a homogeneous structure, the elements of which are tightly glued together with one another. This composite material having at least one external surface made of PVDF and one surface made of a thermoplastic polymer that is incompatible with PVDF is characterized in that both polymers are connected to each other across their surface with a polyalkylmethyrylate that in itself, it is partially and tightly bound to the entire surface of the two polymers to be joined. The contact surfaces of PVDF-polyalkyl methacrylate and the incompatible thermoplastic polymer polyalkyl methacrylate are in the form of an alloy, for example, a mixture of components in a molten state; this form of communication (the components allow to speak about the solidity and homogeneous structure of the composite material as compared to the material called composite-having a heterogeneous structure, which can be obtained, for example, by gluing, in which the contact surface does not represent zones the transition is clearly marked and fragile. The proposed product can also be defined as a COMPOSITE material of the three components formed by the alloy of polyalkyl methacrylate PVDF and polyacrylmethacrylate incompatible polymer with PVDF, and the named material contains at least one external surface of PVDF and one rtb surface of a thermoplastic polymer that is incompatible with P: VDF. One or more of the exterior surfaces of PVDF xaoeate material usually do not contain polyalkylmethacrylate, which serves as a link This composite material, for economic reasons, contains, in particular, only one external surface, and its external surface is made of a thermoplastic polymer that is incompatible with PVDF. However, a thermoplastic polymer that is incompatible with PVDF may serve as a basis for bonding with another material. Thus, it is possible that the composite material according to the invention has two external surfaces of PVDF in accordance with the following sequence of alloys of three components: PVDF polyalkylmethacrylate - a thermoplastic polymer incompatible with PVDF - polyalkylmethacrylate - PVDF. That is why, under the surface made of a polymer incompatible with PVDF, it is meant both the external and internal surfaces. Such a product can be found in all forms of conventional thermoplastics, for example tubes, shells, shaped: products, films, plates (the latter products can be transformed according to known technology, for example by thermal molding) and have at least one external surface in weather conditions and in general form having all the qualities inherent in PVDF, and another surface possessing mechanical properties and in general form in all qualities inherent in thermoplastic polymers, are incompatible stim with PEDFg and has the form of a structurally uniform and homogeneous material. Despite the fact that the thickness of the PVDF layer is not of particular importance, it is advisable, from economic considerations, to make a composite material having a thickness of a PVLF layer. equal from 10 microns to several tens of millimeters. By the term PVDF, not only a homopolymer is raised, but also copolymers containing at least 70 weight% PVDF or a mixture of PVDF with other polymers. Polymethyl methacrylate (PMMA) can be used as polyalkylmethacrylate, the viscosity of which in the molten state can be chosen in the range of the viscous PMMA, and known methods are available, due to which it is possible to bring the existing viscosity to the desired value, for example, by mixing with an insignificant the amount of fillers provided that at least 75% by weight of polyalkyl metacrylate is kept in this mixture. In addition, it is possible to compound by mixing polyalkyl methacrylate e at least one It is another thermoplastic polymer, but it must be ensured that at least 30% by weight of polyalkyl methacrylate is contained in the mixture. Polyalkylmethacrylates miscible polymer may be selected from compounds or classes eleduyuschih Cpd neny: fluorinated thermoplastics chlorinated vinyl polymers, styrenic polymers, polycarbonates, polyurethanes, poly / ate esters segment ethers / copolymers stirolakri onitril-grafted acrylic ela altimeter, copolymers of acrylonitrile butadiene-styrene / polyacrylic esters, such as polymethylacrylate, polyethylacrylate or polybutyl acryl or copolymers of named acrylic esters, for example from vi ylic E, derivatives, or copolymers al kilmetakrilata, e.g., vinyl chloride, vinyl acetate, methyl acrylate, styrene, isobutylene, akri lovoy acid, acrylonitrile and metakrilonitrilom. The thickness of the alkyl polymethacrylate layer varies from a few to 200 microns. In general, it is not advisable to use larger layer thicknesses, which is explained by the effect that polyalkyl methacrylate has on the mechanical properties of the material as a whole. The polymer that is incompatible with PVDF may be a chlorine-containing vinyl polymer, for example, polyvinyl chloride-polyvinylidene chloride, polystyrene or high-impact polystyrene, polycarbonate, polyurethane, styrene-acrylnitrile-grafted acrylic elastomer copolymer, acrylonitrile, and polyacrylne-polystyrene, acrylonitrile, and polyacrylne-polystyrene. The thickness of this polymer layer can be any - from several tens of microns to several millimeters. This thermoplastic polymer may contain fillers / plasticizers, stabilizers, dyes or commonly used, various additives. Example. Three extruders are used. The first of them is equipped with a degassing system, has a diameter of 120 mm and a screw length equal to thirty-three times its diameter. This extruder is used to extrude an acrylonitrile-butadiene-styrene copolymer ABG). The second extruder has a diameter of 50 mm and is intended for polymethacrylate (PMMA), and the third has a diameter of 40 mm and is intended for PVDF. These three extruders feed a stream diffuser cylinder mounted on a flat die of a conventional sample, designed to form a plate approximately 4 NM thick after the calender and a mechanism for drawing a known sample to extrude plates. The ABS viscosity measured at equals 75–10 P with a gradient of 5.6–10–10 P with a gradient of 2 s. The viscosity of the PMMA compound, measured at 200 ° C, is 110-10 N at a velocity gradient of 5.6 to 14-10 at a velocity gradient of 2 seconds. The viscosity of the PVDF compound, measured at, is also 8.8 and 10 P at a velocity gradient of 3.5 and 345 s, respectively. The heating temperatures of the extruders are 190 to 210 s for ABS, 180 to 200 s for PMMA, and 180 to 220 ° C for PVDF. The flow diffuser has a temperature (such as the spinneret). The film is obtained between the cylinders of the calendar; heated to 80 ° C. The total capacity is about 300 kg / h. The GG production of all three extruders is adjusted in such a way as to ultimately obtain a composite material containing an ABS compound layer 4 mm thick, a PMMA compound layer 30 microns thick and a PVDF layer 100 microns thick. These three layers are connected to each other at the exit of the die. After cooling, a composite material having a homogeneous structure is obtained, one of the surface layers of which is made of PVDF and the friend is made of ABS. The interlayer adhesion of MCA is 245 kg / cm. EXAMPLE 2 A flow distributor is used, which allows to obtain a composite material of five layers at the outlet of Flürz, recreate the experience of Example 1 in such a way that the composite material obtained from the polymers mentioned in 1 in the form of plates consisting of layers in a sequence, mkm. from PVDF 75; from PMMA 50; ABS 3 mm; from PMMA 50; from PVDF 75 The resulting composite material contains five layers of hortayo interconnected. After cooling, a composite material is obtained, the surface layers of which are made of PVDF and the internal spy is made of ABS. ISA 245 KG / SM7 Trickery. A twin screw extruder is used for polyvinyl chloride (PVC), an extruder having a diameter of 30 mm for polymethyl methacrylate (PMMA) and an extruder having a diameter of 40 mm for PVDF. The extruders feed the flow diffuser, which is mounted on the top of the tubular protrusion. The mixer under vacuum and the classic drawing system complement the installation. Three extruders are jointly extruded, each of which has a temperature that corresponds to the value at which the extrusion is usually carried out. 1O-200 ° C for PVC, 180-200 C for PMMA and 180-200 C for PVDF. The upper part of the protrusion is maintained in such conditions that the flow diffuser has a temperature of from 195 to. A pipe is obtained, the outer diameter of which is 50 mm, formed successively by a PVC layer of 3 mm thickness, a layer of PMMA with a thickness of about 50 microns and an inner layer of approximately 75 microns thick, made of PVDF. A composite material having a homogeneous and uniform structure is obtained. ISA - 245 kg / s. PRI me R 4. Use a unit containing three valves, similar to those specified in Example 3, completed with a flow diffuser and a tip of a tubular protrusion. In addition, the plant contains syrtem forms and a classic blowing flask, Allowing the joint extrusion of the three polymers to be blown together. PVC is introduced into the first extruder, PMMA - into the second, PVDF - into the third. The temperature in the extruders is 1bO-180 C, I80-l90 c and 190-200 C, respectively, in the flow diffuser and in the exit nozzle. As a result of co-extrusion, a set is obtained, which is blown up using a classical method to obtain a flask. The extruders are located on the flow diffuser in such a way that the resulting flask has an inner layer made of PVDF approximately 100 µm thick, an intermediate layer made of PMMA, approximately 80 µm thick, and an outer layer made of PVC, approximately 8-10 thick mm; All three layers of the flask are well connected to each other from the exit from the upper part of the ledge. After cooling, the flask is a composite product having a homogeneous and uniform structure. MCA 245 kg / cm. EXAMPLE 5. The use of three extruders, the first of which is equipped with a degassing system, has a diameter of 120 mm 1} and a screw length of thirty-three; diameter. The described extruder is used for acrylonitrile-butadiene-styrene (ABS) copolymer, and the second, having a diameter of 50 mm, is used for blends of the following polymers, parts by weight; polymethyl methacrylate (PMMA) 40, PVDF 30; ABS 30. A third extruder having a diameter of 40 mm is used for PVDF. Extruders feed a flow diffuser cylinder, which is mounted on a conventional flat die, designed to produce a plate about 4 mm thick after the calender and sample drawing mechanism known for extruding plates. The viscosity of the ABS compound, measured at, is 75 "10 P with a velocity gradient of 5, b cf and 10" 10 P with a velocity gradient of 2 cG. i The compound viscosity PMMA measured at is 11040 N at a velocity gradient of 5.6 s and 14 10 N at a gradient of speed 2-. The PVDF viscosity measured at is 141–10 and 8.8–10 nfrh with velocity gradients of 3.5 and 354 s, respectively. The extruders have a heating temperature of 190 to 210 s for the ABC compound, 180 to the mixture containing the PMMA compound, and 180 to the PVDF compound. The temperature in the flow diffuser, / as in the spinneret, is 210 ° C. The film is charged between the cylinders of the cable, heated to HRVs. The total capacity is approximately 300 kg / h. The performance of all three extruders is adjusted in such a way as to ultimately get a composite: a material containing a layer made of ABS, 4 mm thick, a layer made of a mixture containing USA, 30 microns THICK, and a layer made of PV | DF / thickness 100 microns Three layers are well coupled with each other from the exit of the die. After cooling, you will receive a composite material having a homogeneous structure, one surface layer of which is made of PVDF and the other is made of LAN.
    .2 ACI - 245 kg / cm
    Example Experience is carried out in. the conditions are similar to those specified in Example 5, however, replace the mixture containing .PMMA with a mixture containing, by weight: PMMA 30; acrylic rubber 40; ABS 30. A composite material is obtained that has a homogeneous structure, the layers of which are well connected between themselves from the exit of the filter, one of the surface layers of which is made of PVDF, and the other is formed of ABS. ISA - 245 kg / cm.
    Example. The method and material of example 1 is used, and the extruder designed for ABS resin servesF for the extrusion of polycarbonate, the other two extruders serve, as in example 1, for the extrusion of PVDF. and SHSHA.
    The extruder heating temperatures are 240-260 ° C for polycarbonate, 200-230 ° C for PMMA and 200-220 for PVF. Diffuser and., Filler have a temperature of 230 C, and the temperature of the cylinder calender.
    Overall capacity adjusted to 100 kg / h. By adjusting the performance of the three extruders, a laminate is formed with a homogeneous structure, one surface of which consists of 200 µm thick PVDF and 5 mm thick of the other polycarbonate layer, the intermediate layer of PMMA having a THICKNESS of about 100 microns. ISA 245 kg / cm
    Example The method is carried out according to Example 1. Polystyrene, PVP and PMMA are co-extruded, temperatures 200-220 s, 180-220 and 180-200c, respectively. The layered material contains a layer of PVHO - 100 microns, of PS 1 mm, of PMMA - 100 microns. ISA 245 kg / cm.
    PRI me R 9 (prototype) .. Layered material obtained by the joint extrusion of polyethylene, a copolymer of ethylene with vinyl acetate and polyvinylidene fluoride. The copolymer contains 24-26% vinyl acetate and 76-74% ethylene. The test results show that the interlayer adhesion is not significant; it is 20-30 kg / cm.
    Thus, the use of PMMA or its mixture with ABS and PAC, or its mixture with acrylic cautch and ABS as an intermediate layer makes it possible to increase the interlayer adhesion from 20 to 245 kg / cm.
    权利要求:
    Claims (1)
    [1]
    LAYERED MATERIAL, including a top layer of thermoplastic. the intermediate adhesive layer and the lower layer of polyvinylidene fluoride, so that in order to increase interlayer adhesion, it contains an upper layer made of a thermoplastic selected from the group consisting of a copolymer of acrylonitrile butadiene styrene, polyvinyl chloride , polycarbonate, polystyrene, and the intermediate layer is made of polymethylmethac-: rylate or a mixture containing 40 parts by weight polymethylmethacrylate, 30 parts by weight a copolymer of acrylonitrile butadiene styrene and 30 parts by weight polyvinylidene fluoride, or a mixture containing 30 parts by weight polymethylmethacrylate, 40 parts by weight acrylic rubber and. 30 parts by weight copolyme. RA acrylonitrile butadiene styrene.
    In CO with
    类似技术:
    公开号 | 公开日 | 专利标题
    US4415519A|1983-11-15|Method of making polyvinylidene fluoride-thermoplastic resin laminates
    US4364886A|1982-12-21|Process for the manufacture of polyvinylidene fluoride - incompatible polymer laminates
    SU1071216A3|1984-01-30|Laminate material
    RU2088616C1|1997-08-27|Composition for coextrusion with polyvinylidene difluoride and composite material based on thereof
    US4107247A|1978-08-15|Method of co-extrusion with foam core
    US3959432A|1976-05-25|Coextrusion process
    US4585701A|1986-04-29|Composites of polyvinylidene fluoride alloys and thermoplastic polymers and their preparation
    US4206165A|1980-06-03|Method of co-extrusion with foam core
    KR100308566B1|2001-11-30|Adhesive binder comprising glutarimide units
    US4291099A|1981-09-22|Polyvinylidene fluoride-polyurethane laminates and method
    US3968196A|1976-07-06|Method of co-extrusion of polyvinylidene fluoride/polystyrene multiple-layered sheeting
    JPH08276548A|1996-10-22|Improvement of composite material containing polyvinylidene fluoride and thermoplastic plastic which is uncompatible with said substance
    JPH0680794A|1994-03-22|Vinylidene fluoride resin film, its use and its production
    CN1069571C|2001-08-15|Extruding thin multiphase polymer film
    US4871506A|1989-10-03|Process for manufacturing films from semi-crystalline fluid polymers by coextrusion and tubular film blowing
    US8377354B2|2013-02-19|Method of producing films by means of coextrusion blow-moulding
    US3275725A|1966-09-27|Method of making laminated tubing
    US3882219A|1975-05-06|Co-extrusion of acrylic ester polymer/polystyrene multiple-layered sheeting
    US3900548A|1975-08-19|Coextrusion of polystyrene and polysulfones
    US7025918B1|2006-04-11|Multilayer structures
    GB2030919A|1980-04-16|Method of making foam core articles
    PL122566B1|1982-08-31|Method of manufacture of thermoplastic composite
    CS219907B2|1983-03-25|Combined three-component material and method of making the same
    KR960010450B1|1996-08-01|Multiple layer film for packaging
    JP2530830B2|1996-09-04|Stretch-molded product of laminate and method for producing the same
    同族专利:
    公开号 | 公开日
    ZA795036B|1980-09-24|
    FR2436676B1|1981-02-13|
    JPH0313059B2|1991-02-21|
    FR2436676A1|1980-04-18|
    JPS5544898A|1980-03-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2443564C2|2007-02-21|2012-02-27|Асахи Гласс Компани, Лимитед|Laminated sheet|US3451876A|1964-05-28|1969-06-24|Ksh Inc|Plastic light-transmitting panel|
    US3565985A|1969-04-10|1971-02-23|Dow Chemical Co|Method of preparing multilayer plastic articles|
    US3647612A|1969-06-06|1972-03-07|Dow Chemical Co|Multilayer plastic articles|
    DE2246497B2|1972-09-22|1976-04-08|Verfahren zum Coextrudieren von thermoplastischem Kunststoff Dynamit Nobel AG, 5210 Troisdorf|PROCESS FOR COEXTRUDING THERMOPLASTIC PLASTIC|
    JPS5651907B2|1974-11-12|1981-12-08|
    JPS5159971A|1974-11-21|1976-05-25|Nippon Carbide Kogyo Kk|TAIKOSEINOSUGURETAFUKUGOFUIRUMU|
    FR2366922A1|1976-10-05|1978-05-05|Sumitomo Chemical Co|Orientated thermoplastic film laminate - produced by compressing between pressure rollers below lowest softening temp. of constituent films|FR2477463B1|1980-03-07|1983-02-11|Ugine Kuhlmann|
    JPH0322301B2|1981-02-28|1991-03-26|Kureha Chemical Ind Co Ltd|
    JPS57187248A|1981-05-12|1982-11-17|Kureha Chemical Ind Co Ltd|Laminate|
    JPH0141500B2|1982-01-25|1989-09-06|Kureha Chemical Ind Co Ltd|
    JPH0157668B2|1983-01-31|1989-12-06|Kanbo Purasu Kk|
    EP0132583B1|1983-08-01|1988-09-14|Ausimont, U.S.A., Inc.|Coextrusion of thermoplastic fluoropolymers with thermoplastic polymers|
    JPH0671785B2|1984-06-23|1994-09-14|電気化学工業株式会社|Method for producing vinylidene fluoride resin-based composite film|
    FR2711665B1|1993-10-25|1995-12-08|Atochem Elf Sa|PVDF adhesion binder, its application as a barrier material and materials obtained from it.|
    WO2005081859A2|2004-02-20|2005-09-09|Saint-Gobain Performance Plastics Corporation|Draw resonant resistant multilayer films|
    US7866348B2|2008-05-01|2011-01-11|Saint-Gobain Performance Plastics Corporation|Multi-layered fuel tubing|
    US8092881B2|2008-05-01|2012-01-10|Saint-Gobain Performance Plastics Corporation|Multi-layered fuel tubing|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7827361A|FR2436676B1|1978-09-25|1978-09-25|
    KR1019790003305A|KR830000832B1|1978-09-25|1979-09-24|Laminates of Polyvinylidene Fluoride and Incompatible Thermoplastics|
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