WO2019052360A1 - Process for injection moulding polymer compounds comprising poly (meth) acrylimide foam particles - Google Patents
Process for injection moulding polymer compounds comprising poly (meth) acrylimide foam particles Download PDFInfo
- Publication number
- WO2019052360A1 WO2019052360A1 PCT/CN2018/103794 CN2018103794W WO2019052360A1 WO 2019052360 A1 WO2019052360 A1 WO 2019052360A1 CN 2018103794 W CN2018103794 W CN 2018103794W WO 2019052360 A1 WO2019052360 A1 WO 2019052360A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thermoplastic resin
- foam particles
- process according
- polymer compound
- injection
- Prior art date
Links
- 239000002245 particle Substances 0.000 title claims abstract description 44
- 229920000642 polymer Polymers 0.000 title claims abstract description 43
- 239000006260 foam Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000001875 compounds Chemical class 0.000 title claims abstract description 25
- 238000001746 injection moulding Methods 0.000 title claims abstract description 19
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 24
- 238000002347 injection Methods 0.000 claims abstract description 10
- 239000007924 injection Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 4
- 238000005187 foaming Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 2
- 229920006152 PA1010 Polymers 0.000 claims description 2
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 2
- 229920006396 polyamide 1012 Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920007790 polymethacrylimide foam Polymers 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- 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
-
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
-
- 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
- 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
- B29K2033/26—Polymers of acrylamide or methacrylamide
-
- 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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
Definitions
- the invention relates to a process for injection 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.
- P (M) I poly (meth) acrylimide
- the present invention provides a process for injection moulding a polymer compound comprising:
- thermoplastic resin which is melt processible at temperatures of less than 400°C.
- said process including steps of:
- 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 injection 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 injection mouldings obtained from the process of the present invention achieves better compressive and/or bend strength than the individual components, besides the light weight.
- the present invention also provides the injection mouldings obtained from the process of the present invention.
- the present invention further provides the use of the injection mouldings of the present invention in light weight design.
- the temperature is 110-180°C, more preferably 120-160°C higher than the T g of the thermoplastic resin.
- the injection pressure is 200-2000 bar, more preferably 200-1500 bar.
- the process is carried out in an injection moulding machine having a screw, an injection nozzle and a mould, and the back pressure of the screw is 0-50 bar, more preferably 10-30 bar.
- the holding pressure is 0-30%, more preferably 0-10%of the injection pressure.
- 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.
- thermoplastic resin constitutes majority of the polymer compound to provide sufficient flowability of the polymer compound for the process of the present invention.
- the thermoplastic resin can constitute 50-99%, preferably 60-95%, more preferably 70-90%
- the P (M) I foam particles can constitute 1-50%, preferably 5-40%, more preferably 10-30%, based on the total weight of the polymer compound.
- 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 120°C, preferably at least 160°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 injection mouldings 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.
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- 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)
- Manufacturing & Machinery (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Provided is a process for injection moulding a polymer compound comprising a thermoplastic resin which is melt processible at temperatures of less than 400°C, and poly (meth) acrylimide (P (M) I) foam particles which maintain the particulate form at a temperature at least 100°C higher than the Tg of the thermoplastic resin. The process includes steps of: (a) heating the polymer compound to a temperature 100-200°C higher than the Tg of the thermoplastic resin, and (b) injecting the polymer compound to a mould under an injection pressure of 100-3000 bar. The injection moulding obtained from the method achieves better mechanical performance than the individual components, and can be widely used in lightweight design.
Description
The invention relates to a process for injection moulding polymer compounds comprising poly (meth) acrylimide (P (M) I) foam particles, in particular polymethacrylimide (PMI) foam particles.
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.
In the past, the P (M) I foams were supplied in the shape of blocks, which however did not quite fit the processing of parts with complex 3D geometries, and could result in long cycle time, low precision, and material waste.
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. However this process still results in long cycle time.
PCT/CN2017/078572 describes a polymer compound comprising poly (meth) acrylimide (P (M) I) foam particles. The present inventors further explored the process for injection moulding the described polymer compound and accomplished the present invention.
Summary of the present invention
The present invention provides a process for injection moulding a polymer compound comprising:
(1) 20-99%a thermoplastic resin, which is melt processible at temperatures of less than 400℃, and
(2) 1-80%poly (meth) acrylimide (P (M) I) foam particles, which maintain the particulate form at a temperature at least 100℃ higher than the T
g of the thermoplastic resin,
based on the total weight of the polymer compound,
said process including steps of:
(a) heating the polymer compound to a temperature 100-200℃ higher than the T
g of the thermoplastic resin where the thermoplastic resin melts and the poly (meth) acrylimide (P (M) I) foam particles maintain the particulate form, and
(b) injecting the polymer compound to a mould under an injection pressure of 100-3000 bar.
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 injection 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.
And it is surprisingly found that the injection mouldings obtained from the process of the present invention achieves better compressive and/or bend strength than the individual components, besides the light weight.
The present invention also provides the injection mouldings obtained from the process of the present invention.
The present invention further provides the use of the injection mouldings of the present invention in light weight design.
Detailed description of the present invention
Preferably, in step a) the temperature is 110-180℃, more preferably 120-160℃ higher than the T
g of the thermoplastic resin.
Preferably, in step b) the injection pressure is 200-2000 bar, more preferably 200-1500 bar.
Preferably, the process is carried out in an injection moulding machine having a screw, an injection nozzle and a mould, and the back pressure of the screw is 0-50 bar, more preferably 10-30 bar.
Preferably, in step b) the holding pressure is 0-30%, more preferably 0-10%of the injection pressure.
There is no limitation to the thermoplastic resin as long as it is melt processible at temperatures of less than 400℃. Melt processible is used in its conventional sense, that the polymer can be processed at the indicated temperatures without substantial degradation of the polymer.
Examples of the thermoplastic resin include polyamides, polyolefins, polyesters and copolymers containing any of the above segments as well as the blend thereof.
Preferably, 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. 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. However, 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℃ 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. The production of such P (M) I foams is 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.
Preferably, 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.
Preferably, the P (M) I foam particles have a grain size which ranges 0.1-30 mm, more preferably 0.5-10 mm.
Preferably, the P (M) I foam particles have a bulk density of 25-220 kg/m
3, more preferably 50-150 kg/m
3.
In one embodiment of the present invention, the P (M) I foam particles are polymethacrylimide (PMI) foam particles.
Preferably, the thermoplastic resin constitutes majority of the polymer compound to provide sufficient flowability of the polymer compound for the process of the present invention.
In such a context, the thermoplastic resin can constitute 50-99%, preferably 60-95%, more preferably 70-90%, and the P (M) I foam particles can constitute 1-50%, preferably 5-40%, more preferably 10-30%, based on the total weight of the polymer compound.
Preferably, the thermoplastic resin is melt processible at temperatures of less than 250℃, and/or the P (M) I foam particles maintain the particulate form at a temperature at least 120℃, preferably at least 160℃ 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.
The injection mouldings 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.
Examples
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℃ 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.
The PMI foam particles were mixed with the melts of a medium-viscosity copolyamide with laurolactam as the main component (T
g = 40℃, commercially available from Evonik Resource Efficiency GMBH under the tradename
N1901) to prepare a 20 : 80 (part by weight) compound, which were 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 the table below. The plates were tested for compressive strength (ISO 844) and bending strength (ISO 178) as well as density. The result is indicated in the table below.
**
200 WF PMI rigid foam, commercially available from Evonik Resource Efficiency GMBH, was also selected as reference material, because of its relatively high compression and bending strength, among the marketed
series of PMI foams.
It can be seen that the injection mouldings of Examples 1-4 achieve higher compressive and/or bending strength than the individual raw materials, in addition to the low density compared with the thermal plastic resin used.
Claims (14)
- A process for injection moulding a polymer compound comprising:(1) 20-99%a thermoplastic resin, which is melt processible at temperatures of less than 400℃, and(2) 1-80%poly (meth) acrylimide (P (M) I) foam particles, which maintain the particulate form at a temperature at least 100℃ higher than the T g of the thermoplastic resin,based on the total weight of the polymer compound,said process including steps of:(a) heating the polymer compound to a temperature 100-200℃ higher than the T g of the thermoplastic resin where the thermoplastic resin melts and the poly (meth) acrylimide (P (M) I) foam particles maintain the particulate form, and(b) injecting the polymer compound to a mould under an injection pressure of 100-3000 bar.
- The process according to claim 1, wherein in step a) the temperature is 110-180℃, preferably 120-160℃ higher than the T g of the thermoplastic resin.
- The process according to any one of the preceding claims, wherein in step b) the injection pressure is 200-2000 bar, preferably 200-1500 bar.
- The process according to any one of the preceding claims, wherein the process is carried out in an injection moulding machine having a screw, an injection nozzle and a mould, and the back pressure of the screw is 0-50 bar, preferably 10-30 bar.
- The process according to any one of the preceding claims, wherein in step b) the holding pressure is 0-30%, preferably 0-10%of the injection pressure.
- The process according to any one of the preceding claims, wherein the thermoplastic resin is selected from polyamides, polyolefins, polyesters and copolymers containing any of the above segments as well as the blend thereof, preferably from aliphatic polyamides, more preferably from the group consisting of PA6, PA11, PA12, PA46, PA66, PA10, PA610, PA612, PA1010, PA1012 and the blend thereof.
- The process according to any one of the preceding claims, wherein the P (M) I foam particles have a grain size which ranges 0.1-30 mm, preferably 0.5-10 mm, and /or a bulk density of 25-220 kg/m 3, preferably 50-150 kg/m 3.
- The process according to any one of the preceding claims, wherein the P (M) I foam particles are obtained by the granulation of P (M) I foams which are not in particulate form, or the foaming of P (M) I polymer particles.
- The process according to any one of the preceding claims, wherein the P (M) I foam particles are polymethacrylimide (PMI) foam particles.
- The process according to any one of the preceding claims, wherein the polymer compound comprises:50-99%, preferably 60-95%, more preferably 70-90%the thermoplastic resin, and1-50%, preferably 5-40%, more preferably 10-30%the P (M) I foam particles,based on the total weight of the polymer compound.
- The process according to any one of the preceding claims, whereinthe thermoplastic resin is melt processible at temperatures of less than 250℃,and/orthe P (M) I foam particles maintain the particulate form at a temperature at least 120℃, preferably at least 160℃ higher than the T g of the thermoplastic resin.
- The process according to any one of the preceding claims, wherein the polymer compound is in situ made in step a) by physically mixing the P (M) I foam particles and the melt of the thermoplastic resin.
- Injection mouldings obtained from the process according to any one of the preceding claims.
- Use of the injection mouldings according to claim 13 in light weight design.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNPCT/CN2017/102026 | 2017-09-18 | ||
| CN2017102026 | 2017-09-18 |
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| WO2019052360A1 true WO2019052360A1 (en) | 2019-03-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2018/103794 WO2019052360A1 (en) | 2017-09-18 | 2018-09-03 | Process for injection moulding polymer compounds comprising poly (meth) acrylimide foam particles |
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| Country | Link |
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| WO (1) | WO2019052360A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115141306A (en) * | 2022-08-11 | 2022-10-04 | 河南同胜新材料科技有限公司 | Polymethacrylimide foamed plastic and preparation method thereof |
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| KR20150067743A (en) * | 2013-12-10 | 2015-06-18 | 주식회사 엘지화학 | Thermoplastic resin composition having exellent chemical resistantce and molded article prepared therefrom |
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| JPH05111933A (en) * | 1991-10-22 | 1993-05-07 | Daicel Chem Ind Ltd | Production of molded form of hardening resin |
| CN101611083A (en) * | 2007-01-30 | 2009-12-23 | 赢创罗姆有限责任公司 | The moulding compound that is used for delustring PMMI moulded product |
| CN102958662A (en) * | 2010-07-30 | 2013-03-06 | 赢创工业集团股份有限公司 | In-mould-foaming process using foamable medium with outer layers, and plastics moulding obtainable therefrom |
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| CN115141306A (en) * | 2022-08-11 | 2022-10-04 | 河南同胜新材料科技有限公司 | Polymethacrylimide foamed plastic and preparation method thereof |
| CN115141306B (en) * | 2022-08-11 | 2023-08-08 | 河南同胜新材料科技有限公司 | Polymethacrylimide foam plastic and preparation method thereof |
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