[go: up one dir, main page]

WO2019062731A1 - Procédé de moulage par extrusion de composés polymères comprenant des particules de mousse de poly(méth)acrylimide - Google Patents

Procédé de moulage par extrusion de composés polymères comprenant des particules de mousse de poly(méth)acrylimide Download PDF

Info

Publication number
WO2019062731A1
WO2019062731A1 PCT/CN2018/107456 CN2018107456W WO2019062731A1 WO 2019062731 A1 WO2019062731 A1 WO 2019062731A1 CN 2018107456 W CN2018107456 W CN 2018107456W WO 2019062731 A1 WO2019062731 A1 WO 2019062731A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
foam particles
process according
polymer compound
meth
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.)
Ceased
Application number
PCT/CN2018/107456
Other languages
English (en)
Inventor
Ricardo Luiz Willemann
Qianwen KONG
Denis HOLLEYN
Zhenyuan SHI
Kaifeng YAN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Specialty Chemicals Shanghai Co Ltd
Original Assignee
Evonik Specialty Chemicals Shanghai Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Evonik Specialty Chemicals Shanghai Co Ltd filed Critical Evonik Specialty Chemicals Shanghai Co Ltd
Publication of WO2019062731A1 publication Critical patent/WO2019062731A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • 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
    • B29C44/36—Feeding the material to be shaped
    • B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
    • B29C44/44—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form
    • B29C44/445—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form in the form of expandable granules, particles or beads
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • B29C67/207—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising impregnating expanded particles or fragments with a binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate

Definitions

  • the invention relates to a process for extrusion moulding polymer compounds comprising poly (meth) acrylimide (P(M) I) foam particles, in particular polymethacrylimide (PMI) foam particles.
  • P(M) I poly (meth) acrylimide
  • PMI polymethacrylimide
  • Poly (meth) acrylimide foams e.g. polymethacrylimide foams, such as those marketed under the trademark by Evonik Resource Efficiency GMBH, are widely used in composite material for light weight design in the aerospace, automotive, sport and medical device industries, etc. due to their light weight and high mechanical performance.
  • WO2013/056947 describes a mould shaping process of P (M) I foams which partially solves the above problems, wherein (prefoamed) P (M) I polymer particles are foamed in a mould with the aid of adhesives, which can be a polyamide or a poly (meth) acrylate.
  • the dose of the adhesives can be up to 20%of the P (M) I polymer particles, i.e. up to 16.7%based on the total weight of the P (M) I polymer particles and the adhesive.
  • This process still results in long cycle time.
  • PCT/CN2017/078572 describes a polymer compound comprising poly (meth) acrylimide (P (M) I) foam particles.
  • PCT/CN2017/102026 describes a process for injection moulding the polymer compound. The present inventors further explored the process for extrusion moulding the polymer compound and accomplished the present invention.
  • the present invention provides a process for extrusion moulding a polymer compound comprising:
  • thermoplastic resin which is melt processible at temperatures of less than 400°C.
  • T g refers to glass transition temperature, which can be determined by the DSC method according ISO 1135.
  • the present inventor has found it is important to control the temperature and pressure during the extrusion moulding process so as to provide sufficient flowability of the polymer compound, and to avoid the damage of the cell structure of the foam particles.
  • the extrudate obtained from the process of the present invention can achieve light weight. And it is surprisingly found that the same light weight can be achieved with less P (M) I foam load in the polymer compound in the present invention, compared with an injection moulding process.
  • the present invention also provides the extrudate obtained from the process of the present invention.
  • the present invention further provides the use of the extrudate of the present invention in light weight design.
  • the temperature is 130-220°C, more preferably 140-200°C higher than the T g of the thermoplastic resin.
  • the extrusion pressure is 10-200 bar, preferably 10-100 bar.
  • the extrudate is in the form selected from profiles, sheets, films, tubes, cylinders, cubes, rods, ribbons and meshes.
  • thermoplastic resin there is no limitation to the thermoplastic resin as long as it is melt processible at temperatures of less than 400°C. Melt processible is used in its conventional sense, that the polymer can be processed at the indicated temperatures without substantial degradation of the polymer.
  • thermoplastic resin examples include polyamides, polyolefins, polyesters and copolymers containing any of the above segments as well as the blend thereof.
  • the polyamide is selected from aliphatic polyamides, more preferably PA6, PA11, PA12, PA46, PA66, PA10, PA610, PA612, PA1010, PA1012 and the blend thereof.
  • the P (M) I foam particles used in the present invention can be obtained by the granulation of the P (M) I foams which are not in particulate form.
  • the P (M) I foams are also termed rigid foams, and feature particular robustness.
  • the P (M) I foams are normally produced in a two-stage process: a) production of a cast polymer, and b) foaming of said cast polymer. In accordance with the prior art, these are then cut or sawn to give the desired shape.
  • Production of the P (M) I foams begins with production of monomer mixtures which comprise (meth) acrylic acid and (meth) acrylonitrile, preferably in a molar ratio of from 2: 3 to 3: 2 as main constituents.
  • monomer mixtures which comprise (meth) acrylic acid and (meth) acrylonitrile, preferably in a molar ratio of from 2: 3 to 3: 2 as main constituents.
  • Other comonomers can also be used, examples being esters of acrylic or methacrylic acid, styrene, maleic acid and itaconic acid and anhydrides thereof, and vinylpyrrolidone.
  • the proportion of the comonomers here should not be more than 30%by weight.
  • Small quantities of crosslinking monomers can also be used, an example being allyl acrylate. However, the quantities should preferably be at most from 0.05%by weight to 2.0%by weight.
  • the copolymerization mixture moreover comprises blowing agents which at temperatures of about 150 to 250°C either decompose or vaporize and thus form a gas phase.
  • the polymerization takes place below this temperature, and the cast polymer therefore comprises a latent blowing agent.
  • the polymerization advantageously takes place in a block mould between two glass plates.
  • the cast polymer is then foamed at an appropriate temperature in a second step.
  • P (M) I foams are known in principle to a person skilled in the art and can be reviewed in EP 1 444 293, EP 1 678 244 or WO 2011/138060 for example.
  • the P (M) I foam particles used in the present invention can also be obtained by the foaming of the P (M) I polymer particles.
  • the P (M) I polymer particles can be obtained by grinding the cast polymer, for example, in a cutting mill. The grindings are then foamed at an appropriate temperature to produce the P (M) I foam particles.
  • the P (M) I foam particles used in the present invention is obtained by the foaming of the P (M) I polymer particles, where the closed foam cells are not destroyed, compared with the P (M) I foam particles obtained by the granulation of the P (M) I foams.
  • the P (M) I foam particles have a grain size which ranges 0.1-30 mm, more preferably 0.5-10 mm.
  • the P (M) I foam particles have a bulk density of 25-220 kg/m 3 , more preferably 50-150 kg/m 3 .
  • the P (M) I foam particles are polymethacrylimide (PMI) foam particles.
  • PMI polymers and/or foams commercially available from Evonik Resource Efficiency GMBH, may be mentioned in particular.
  • the polymer compound comprises
  • thermoplastic resin 30-99%, more preferably 40-99%the thermoplastic resin, and,
  • the thermoplastic resin is melt processible at temperatures of less than 250°C, and/or the P (M) I foam particles maintain the particulate form at a temperature at least 140°C, preferably at least 180°C higher than the T g of the thermoplastic resin.
  • the polymer compound of the present invention may include additives, such as calcium carbonate, glass beads, zinc oxide, and fiber reinforcements such as ceramic fibers, aramid fibers, potassium titanate fibers, glass fibers and carbon fibers, depending on the effect or performance desired.
  • additives such as calcium carbonate, glass beads, zinc oxide, and fiber reinforcements such as ceramic fibers, aramid fibers, potassium titanate fibers, glass fibers and carbon fibers, depending on the effect or performance desired.
  • the extrudates obtained from the process of the present invention are generally suitable in principle for any type of lightweight design, and can in particular be used in mass production by way of example for structural parts in the automobile industry, in rail vehicle construction or shipbuilding, in the aerospace industry, in mechanical engineering, in the production of sports equipment, in furniture construction or in the design of wind turbines.
  • the PMI foam particles used in the examples were prepared from PMI polymer particles marketed with trademark Triple F by Evonik Resource Efficiency GMBH.
  • the PMI polymer particles were produced from a fully polymerized copolymer sheet (which had not been prefoamed) with the aid of a granulator.
  • the grain size range of the particles used in the examples, after sieving to keep the fines, was below 1.0 mm.
  • the bulk density of the PMI polymer particles was about 600-700 kg/m 3 .
  • the PMI polymer particles were foamed in an oven at a temperature of 200-240°C for 30-60 mins.
  • the obtained PMI foam particles had a bulk density of 100-150 kg/m 3 and a grain size of 0.5-5 mm.
  • Example 1 was a reference where only the polyamide of L1600 was shaped.
  • Example 4 An injection moulding specimen with a density close to Example 4 was also prepared for comparison.
  • the PMI foam particles were mixed with the melts of a PA12 ( L1600, commercially available from Evonik Resource Efficiency GMBH) to prepare a compound, which was shaped into plates having a thickness of 5 mm by injection moulding in an injection machine (Engel Victory 200/110 Tech Pro) according to process parameters indicated in Table 2 below.
  • a PA12 L1600, commercially available from Evonik Resource Efficiency GMBH
  • the specimen was tested for density (ISO 1183) and the result is also indicated in Table 2 below.
  • the load of PMI foam particles in the polymer compound reaches 50%for the moulding part obtained by an injection moulding process to achieve a density of 0.73 g/cm 3
  • the load of the PMI foam particles is 7.5%to achieve a density of 0.71 g/cm 3
  • the extrusion moulding process of the present invention would need much less load of the PMI foam particles to achieve the same light weight effect compared with an injection moulding process.
  • extrusion moulding is a continuous process. It is believed that the extrusion moulding process of the present invention would be more time efficient to achieve the same light weight than an injection moulding process.
  • Example 10 was a reference where only the PA12 composition of LX9012 (commercially available from Evonik Resource Efficiency GMBH) was shaped.
  • the extrusion moulding process of the present invention also works with polymer compound with high foam load (e.g. 60%) and the obtained extrudates achieve very significant low weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un procédé de moulage par extrusion d'un composé polymère comprenant une résine thermoplastique qui peut être traitée à l'état fondu à des températures inférieures à 400°C et des particules de mousse de poly(méth)acrylimide (P(M)I) qui conservent la forme particulaire à une température supérieure d'au moins 120℃ à la T g de la résine thermoplastique. Le procédé comprend les étapes consistant à: (a) chauffer le composé polymère à une température supérieure de 120-240℃ à la T g de la résine thermoplastique et (b) mouler par extrusion le composé polymère dans un moule dans des conditions de pression d'extrusion de 5-300 bars pour obtenir un extrudat. L'extrudat obtenu au moyen du procédé de la présente invention atteint un poids léger significatif par comparaison avec la référence, et peut être largement utilisé dans une conception légère.
PCT/CN2018/107456 2017-09-28 2018-09-26 Procédé de moulage par extrusion de composés polymères comprenant des particules de mousse de poly(méth)acrylimide Ceased WO2019062731A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNPCT/CN2017/104010 2017-09-28
CN2017104010 2017-09-28

Publications (1)

Publication Number Publication Date
WO2019062731A1 true WO2019062731A1 (fr) 2019-04-04

Family

ID=65900579

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/107456 Ceased WO2019062731A1 (fr) 2017-09-28 2018-09-26 Procédé de moulage par extrusion de composés polymères comprenant des particules de mousse de poly(méth)acrylimide

Country Status (1)

Country Link
WO (1) WO2019062731A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3978215A1 (fr) * 2020-09-30 2022-04-06 Evonik Operations GmbH Fabrication de moules à noyau en mousse complexes pourvus de surfaces de classe a
US12496753B2 (en) 2020-08-18 2025-12-16 Evonik Operations Gmbh Production of high temperature polymer based pellets by underwater pelletization at elevated water temperature to produce (rigid) bead foams

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101857656A (zh) * 2010-05-24 2010-10-13 四川大学 用于生产聚甲基丙烯酰亚胺泡沫材料的可发性颗粒及应用
CN103923337A (zh) * 2014-04-30 2014-07-16 湖南兆恒材料科技有限公司 聚甲基丙烯酰亚胺复合泡沫吸波材料
WO2015071239A1 (fr) * 2013-11-15 2015-05-21 Evonik Industries Ag Structures en nid d'abeilles remplies de mousse de poly(méth)acrylimide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101857656A (zh) * 2010-05-24 2010-10-13 四川大学 用于生产聚甲基丙烯酰亚胺泡沫材料的可发性颗粒及应用
WO2015071239A1 (fr) * 2013-11-15 2015-05-21 Evonik Industries Ag Structures en nid d'abeilles remplies de mousse de poly(méth)acrylimide
CN103923337A (zh) * 2014-04-30 2014-07-16 湖南兆恒材料科技有限公司 聚甲基丙烯酰亚胺复合泡沫吸波材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12496753B2 (en) 2020-08-18 2025-12-16 Evonik Operations Gmbh Production of high temperature polymer based pellets by underwater pelletization at elevated water temperature to produce (rigid) bead foams
EP3978215A1 (fr) * 2020-09-30 2022-04-06 Evonik Operations GmbH Fabrication de moules à noyau en mousse complexes pourvus de surfaces de classe a

Similar Documents

Publication Publication Date Title
CN102958662A (zh) 使用可发泡介质和覆盖层的模内发泡方法和可由其获得的塑料模制品
US20200376714A1 (en) Micro-particle-size thermoplastic micro-airbag polyurethane elastomer material and preparation therefor
US20200165401A1 (en) Thermoplastic micro-sac polymer elastomer material and preparation method therefor
WO2019062731A1 (fr) Procédé de moulage par extrusion de composés polymères comprenant des particules de mousse de poly(méth)acrylimide
CN111253677A (zh) 一种低密度聚丙烯珠粒泡沫、其制备方法及应用
CN114454375B (zh) 发泡成型体的制造方法
CN106061702A (zh) 回收可发性塑料材料的工艺以及可由此获得的可发性塑料材料或膨胀的塑料材料
KR20170117537A (ko) 열가소성 폴리우레탄에 기초한 폼의 제조 방법
CN108219326A (zh) 一种高抗冲pvc管材配方及其制备方法
KR102340431B1 (ko) 폴리(메트)아크릴이미드 발포체 입자를 포함하는 중합체 화합물
US7807088B2 (en) Polyvinylidene fluoride resin powder for melt molding and process for producing molding from the resin powder
CN105082690A (zh) 含泡沫芯层的纤维增强热塑性复合材料构件及其制备方法
JPH07164434A (ja) 重合α−オレフィン樹脂を配合する方法
WO2019052360A1 (fr) Procédé de moulage par injection de composés polymères comprenant des particules de mousse de poly(méth)acrylimide
JP3929497B2 (ja) フルオロポリマーの押出発泡成形
WO2019155747A1 (fr) Corps en mousse d'homopolymère de fluorure de vinylidène et procédé de production de corps en mousse
TW202231755A (zh) 製造可撓性發泡體之方法、由該方法製成之發泡體及包括該發泡體的物品
CN101250282A (zh) 一种聚丙烯发泡装饰材料挤出装置及生产工艺
US12138845B2 (en) Molded resin body production method
JP4261676B2 (ja) 再生発泡性スチレン系樹脂粒子の製造法
CN109294145B (zh) Ps/asa合金组合物和ps/asa合金材料及其应用
Zubair et al. Polymeric Materials
CN102604313A (zh) Sbs交联弹性体复合材料及其制备方法
CN109852045B (zh) 一种微孔发泡长碳纤维增强pa11材料及其制备方法
SU1699793A1 (ru) Способ получени изделий из термопластичных композиций

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 04/09/2020)

122 Ep: pct application non-entry in european phase

Ref document number: 18860433

Country of ref document: EP

Kind code of ref document: A1