CN104245268A - Method for producing polyamide molded bodies from a polymerizable composition by means of a rotational molding process - Google Patents

Method for producing polyamide molded bodies from a polymerizable composition by means of a rotational molding process Download PDF

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Publication number
CN104245268A
CN104245268A CN201380017044.9A CN201380017044A CN104245268A CN 104245268 A CN104245268 A CN 104245268A CN 201380017044 A CN201380017044 A CN 201380017044A CN 104245268 A CN104245268 A CN 104245268A
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China
Prior art keywords
polymerisable compound
aforementioned
lactams
mould support
temperature
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CN201380017044.9A
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Chinese (zh)
Inventor
S·比达塞克
P·德斯保斯
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BASF SE
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BASF SE
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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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C08G69/18—Anionic polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/24—Pyrrolidones or piperidones
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material

Abstract

The invention relates to a method for producing polyamide molded bodies, wherein a polymerizable composition containing lactam is subjected to a rotational molding process.

Description

Prepared the method for polyamide molding body by polymerisable compound by rotomoulding
Explanation
The present invention relates to a kind of method preparing polyamide molding body by making the polymerisable compound rotational molding containing lactams.
Thermosetting polymer such as polyurethane or polyester are once hardening, and just can not change their shape again, these are different from thermoplastic polymer, and the process of the heating of thermoplastic polymer, distortion and cooling is all reversible.Often be not only polyamide by the thermoplastic polymer used in the industry, also comprise polyethylene, polypropylene, Merlon etc.
Current polyamide is by dicarboxylic acids or their derivative and diamines condensation substantially, or is prepared by the ring-opening polymerisation of lactams.Also has the method being prepared polyamide by the anion implementing anionic lactam polymerisation of activation known in principle.The ring-opening polymerisations in the anionic polymerisation of base catalysis such as lactams such as caprolactam, lauric lactam, piperidones, pyrrolidones.This is normally at high temperature, by be formed by lactams and the melt comprising base catalyst and activator (or co-catalyst or initator) carries out being polymerized realizing.
Describe as an example in DE-A 14 20 241 under the existence of the potassium hydroxide as catalyst, use two (N, the N-dibutyl-urea groups) hexane of 1,6-as activator, the anionic polymerisation of the lactams carried out.The reaction of the anion implementing anionic lactam polymerisation of the activation of sodium caprolactam is used to be described in Polyamide as an example, Kunststoff Handbuch [Polyamides, Plastics Handbook], volume 3/4, ISBN3-446-16486-3,1998, Carl HanserVerlag, 49-52 page and Macromolecules, volume 32,23rd phase (1999), the 7726th page.
The solid particle comprising lactams, catalyst and activator is described in undocumented EP 11176950.1 and EP 11172731.9.These monomer compositions prepare polyamide by the anionic polymerisation of activation.Described particle is prepared by spraying dry, if the form of aggregate then optionally carries out process of lapping again.The solid particle described in undocumented EP 12151670.9 also can comprise catalyst, activator, unfunctionalized and/or hydroxy-end capped rubber except lactam component.
Prior art is also thought during polymer in-mold plastomer molding, the anionic polymerisation of lactams can occur in reaction moulding process or in reaction implanbation moulding process, wherein in the process of reaction, catalyst and other optional additives join in lactams melt.The anionic polymerisation of the lactams in such reaction moulding process or in reaction implanbation moulding process causes very large technical costs.First, bicomponent system must be mixed before the use.Then also need other equipment to prepare melt, such as, mixer, mixing nozzle etc., these have been connected on existing polymerization mould (mold).When a melt is used, before melt is introduced in existing polymeric molds, also can not stop some generations be polymerized, therefore must carry out extra cleaning step to the equipment used after the activation.
Polymer in-mold plastomer is prepared by thermoplastic polymer from prior art is known.Rotomolding processes is a kind of such plastic method.In this approach, the raw material comprising polymer is filled into a kind of mould support (mold support) (rotational molding mould), heating mould support dual-axis rotation (biaxial rotation).The polymer uniform of melting is distributed on the inwall of mould support.After the cooling period, the polymer in-mold plastomer (Handbook of Thermoplastic Elastomers, the Drobny that make is removed, Jiri George, 2007,108-121, William Andrew Publishing/Plastics Design Library).
The polymer in-mold plastomer prepared by rotomolding processes can be manufactured to diversified shape.Compare with injection molding methods, the method for rotational molding can provide more shape.Such as, shape can be specific, thus can introduction hole or the pattern (cutouts) that cuts on polymer in-mold plastomer simply.This compares with extrusion method is also an advantage.Rotational molding also can manufacture thin-walled moulding bodies.But relative to extrusion method or injection molding methods, the decisive advantage of rotomolding processes can highly save the cost preparing moulding bodies.
Rotational Molding Technology, Crawford, Roy J.; Throne, James L.; 2007; William Andrew Publishing/Plastics Design Library, describes the mode moulded polyamide by rotational molding, especially polycaprolactam in the 40th page.
US 4,729, describe a kind of preparation of heat-stabilised poly amide compositions in 862, this composition is made up of polyamide and cupric iodide.Two described components mix at 282 DEG C.Then mixture is used for rotomolding processes.
The method of rotational molding normally introduces polymer to mould support, under agitation melt polymer, to obtain required shape.This process has a lot of shortcoming.Mould support must be heated to the fusing point of polymer, sometimes needs higher temperature, and this depends on the polymer of use.Such as, temperature >200 DEG C is usually needed to be transformed into liquid condition to make PA6.Even if like this, can not always ensure to form improving uniformity of melt.This causes a large amount of mass defects of gained polyamide molding body.Such as, the existence in undesirable hole on moulding bodies can not always be avoided.In addition, due to higher viscosity and fragility, PA becomes more difficult man-hour adding.In order to obtain equally distributed polymer melt in rotational molding mould, need sufficient rotation time.This will postpone the preparation of moulding bodies, allow this method not have advantage economically.
Describe in JP 7032390 and prepare moulding bodies by the mode of rotational molding, wherein under a kind of anionic polymerization catalyst and a kind of activator exist, ω-implementing anionic lactam polymerisation.
Describe the preparation of moulding bodies in GB 1133840, wherein under rotation, lactams is polymerized in the mould of hollow.To this, first provide a kind of melt of activation, then transferred in the mould carrying out polymerisation.
Describe the method for rotational molding in IE 991090, wherein especially lactams and activator can be filled into mould as pre-composition.
Describe a kind of method of being polymerized the ducted body being prepared molding by polyamide by rotational molding by the activated anionic of caprolactam in US 3780157, wherein moulding bodies is by inorganic filler, especially glass filler strengthening.Although its 2nd hurdle the 60 to 67 row describes a kind of mixture of powders be usually made up of component lactams, catalyst and activator and can be introduced in mould carrier, first specific embodiment display provides a kind of activation lactams melt, and it is transferred in rotational molding mould in the blown state.
Describe in EP 0755966 and prepare composite by the reinforcing fiber in PA-12 matrix (matrix), described PA-12 matrix is made up of the lauric lactam of anionic polymerisation, in D2, also be the lauric lactam melt first preparing a kind of activation, be filled into liquid condition in the rotational molding mould of heat.Melt is in pressurization and lower polymerization of heating.But D2 also discloses, and (the 4th page, 37/38 row) can use the mixture of powders be made up of lactams, catalyst and co-catalyst.
Preparation and the use of the polymeric compositions be made up of polymeric precursors, a kind of catalyst and a kind of activator is described in US 2007/0246475.Mixture is melt, is filled in rotational molding mould in a liquid state, then can be polymerized and rotational molding simultaneously.But shortcoming is that user not only has more operation, that is prepares the melt of polymeric precursors, catalyst and activator, and also need heatable mixer except rotational molding system.For being prepared separately storing and separating higher auxiliary (logistic) cost of traffic requirements of the parent material of the method for polyamide by activated anionic implementing anionic lactam polymerisation.Similarly, separately introduce raw material and will have higher equipment cost in the process being prepared polyamide by activated anionic implementing anionic lactam polymerisation.
When---a kind of melt comprises activator, another comprises catalyst---is mixed with each other to provide polymeric compositions needs by two kinds of raw material melts, the stability of polymeric compositions to polymerization always can not ensured.Raw material melt mainly mixes or combination in pipeline or by a kind of online (in-line) blender or a kind of mixing nozzle.Even if before transferring to rotational molding mould, also produce the no longer stable reactant mixture of polymerization.Once reaction melt has been transferred in rotational molding mould, need all equipment of extra cleaning contact melt, otherwise residual melt is still in polymerization, this will cause sedimentary formation, and the worst situation is occluding device.
Surprisingly, find by providing a kind of solid polymerizable composition containing lactams, and use it to be polymerized and plastotype simultaneously, polyamide molding body can be prepared by the method for rotational molding.This not only avoids the above-mentioned shortcoming that prior art prepares polyamide molding body, and the enforcement of this method more can save time and energy consumption.Advantageously be filled on mould support or the material be coated on mould support is not directly abundant polymeric polyamide but liquable at low temperatures precursor, and polymerisation original position is implemented.In the process of preparation, this method not only can save time, and also can reduce energy consumption, because the component preparing moulding bodies only once must be heated to above the temperature of monomer fusing point usually.
Another advantage about method economy is that the preparation of polyamide molding body can use polymerisable composition, it has comprised lactam monomers, catalyst and activator, optionally other additives, it can such as directly be polymerized as on a yarn fabric support by increasing temperature in a mold or on support.The described polymerisable compound used in invention can be filled into mould support (rotational molding mould) in the solid state, becomes flowable liquid wherein, distributes and be polymerized, obtain polyamide molding body.
Owing to directly can prepare the composition of one-component in the place of consumer, the height therefore reduced for the preparation of the art methods of polyamide molding body is assisted and equipment cost.Therefore, also can prepare a kind of polymerisable compound of commercial form, and stable precursor is transported to prepares in ultimate consumer's hand of moulding bodies.
The invention provides a kind of method for the preparation of polyamide molding body, wherein:
A () provides a kind of polymerisable compound, comprising:
A) at least one lactams;
B) at least one catalyst, and;
C) at least one activator, is selected from isocyanates, acid anhydrides, acyl halide, itself and A) product, and their mixture,
(b) step a) in the polymerisable compound that provides can be added in the mould support of rotational molding system by liquid form with solid,
C () polymerisable compound under rotation in heating mould support is the temperature of flowable liquids to polymerisable compound, and described flowable liquids polymerisable compound distributes equably,
(d) under rotation, polymerizing polymerizable composition,
The composition of (e) cooling polymerization, and
F polyamide molding body shifts out by () from mould support.
The present invention also provides the polymerisable compound comprising at least component A, B and C for preparing the purposes of polyamide molding body in rotational molding.
Compare with the known method of prior art, the feature of the inventive method has following in some one at least:
The efficient time uses
Efficient energy uses
Devices with low cost
Higher polyamide molding weight
The content of monomer of low remnants.
For object of the present invention, statement " polymerisable compound " means at the standard conditions the composition that (20 DEG C, 1013 millibars) are at room temperature solids.The polymerisable compound that preferred the present invention uses at high temperature is still solid.The polymerisable compound used in the present invention preferably at least 50 DEG C, especially preferably the temperature of at least 60 DEG C be still solid.
For object of the present invention, statement " mould support " is meant to a kind of rotational molding mould.
For object of the present invention, statement " melt " also refers to the lactams melted, and is wherein dissolved with activator and catalyst.For object of the present invention, statement " fusing " is not strict interpretation in physical chemistry meaning, but be transformed into the liquid synonym that can flow.
For object of the present invention, statement " dual-axis rotation " refers to the rotation round vertical and trunnion axis.
A kind of polymer is " dimensionally stable " when being no longer flowable liquid.
It is known in principle for preparing polyamide by activated anionic polymerization.In the method for the invention, the catalyst being preferred for anionic polymerisation is the compound allowing lactam anion to be formed.Lactam anion itself has the function identical with catalyst.
Polymerisable compound preferably takes the form of particle.
Polymerisable compound especially takes the form of particle, and it has identical composition substantially, and wherein particle all comprises component A), B) and C).For object of the present invention, the composition that " substantially the same composition " is meant to particle is identical, such as, except the deviation produced due to production process, when these usually occur in weighing or measuring of the composition forming particle.Therefore each single particle comprises the whole compositions for polymerisation.The particle especially without identical composition only comprises composition A), B) and one C), or only comprise two kinds.Therefore the polymerisable compound used in granular form in the present invention is fundamentally different from the polymerisable compound (being known as dry blend) of drying preparation well known in the prior art.
The average diameter of particle normally 1 to 2000 μm, preferably 10 to 1000 μm, especially preferably 50 to 500 μm, very especially preferably 100 to 200 μm.Average diameter can measure by light scattering or by screening (sieve fractions), is volume averaging (volume-average) diameter.
A kind of polymerisable compound of preferred use, based on the total weight of composition, it comprises 50 to 99.7 weight portions, preferably 70 to 98 weight portions, especially preferably at least one lactams (A) of 80 to 95 weight portions.
A kind of polymerisable compound of preferred use, based on the total weight of composition, it comprises 0.2 to 16 weight portion, preferably 2.4 to 8 weight portions, especially preferably at least one activator (C) of 3.2 to 5.6 weight portions.
A kind of polymerisable compound of preferred use, based on the total weight of composition, it comprises 0.1 to 5.4 weight portion, preferably 0.54 to 3.6 weight portion, especially preferably at least one catalyst (B) of 0.64 to 3 weight portion.
At room temperature, step a) in the polymerisable compound that provides be stable solid.Especially, the polymerisable compound used in the present invention is not polymerized when the fusing point lower than lactams composition, and the polymerisable compound therefore used is all stable for any unwanted too early polymerisation.
The polymerisable compound used in the present invention can store the several months, can at any required time for the preparation of polyamide.
Especially suitable lactams is epsilon-caprolactams, 2-piperidones (δ-valerolactam), 2-Pyrrolidone (butyrolactam), spicy inner formyl amine, oenantholcatam (enantholactam), lauric lactam and their mixture.Preferred caprolactam, lauric lactam, and their mixture.As lactams, especially preferably only use caprolactam or only use lauric lactam.
In addition, polymerisable compound except at least one lactams, also can comprise at least one can with the monomer of its copolymerization (M).Monomer (M) can be selected from lactone and crosslinking agent in principle.Monomer is preferably selected from lactone.Preferred lactone is such as 6-caprolactone and/or gamma-butyrolacton.The amount of monomer (M) should more than 40 % by weight, based on the total weight using monomer in polymerisation.Preferably the ratio of (M) is 0 to 30 % by weight, preferably 0.1 to 20 % by weight, and based on total monomer.The polymerisable compound used in the present invention can comprise a kind of cross-linking monomer.A kind of cross-linking monomer can be comprise more than a kind of can with the compound of the group of lactam monomers copolymerization.The example of this type group is epoxy radicals, amine, carboxyl, acid anhydrides, oxazoline, carbodiimide, urethane, isocyanates and lactams group.The example of suitable cross-linking monomer is the amino lactams replaced, such as, aminocaproic lactam, amino piperidine hydrochloride, aminopyrrolidone, aminocaproic lactam, amino oenantholcatam, amino lauric lactam, with their mixture, preferred aminocaproic lactam, aminopyrrolidone and their mixture, especially preferably aminocaproic lactam.
In a preferred embodiment of the invention, lactams is uniquely by the monomer used.
The suitable catalyst B used in the inventive method) be the catalyst often used, such as those are through being usually used in the catalyst of anionic polymerisation.
This kind of catalyst is such as known in Polyamide, Kunststoffhandbuch [Polyamides, Plastics Handbook], 1998, Karl HanserVerlag.Catalyst B) be preferably selected from sodium caprolactam (sodium caprolactamate), caprolactam potassium, caprolactam magnesium bromide (magnesium bromide caprolactamate), caprolactam magnesium chloride (magnesium chloride caprolactamate), dicaprolactam magnesium (magnesium biscaprolactamate), sodium hydride, sodium, NaOH, sodium methoxide, caustic alcohol, normal propyl alcohol sodium, sodium butoxide, hydrofining, potassium, potassium hydroxide, potassium methoxide, potassium ethoxide, normal propyl alcohol potassium, butanols potassium and their mixture.
Especially the catalyst B being selected from sodium hydride, sodium and sodium caprolactam is used).Particularly preferably use the catalyst B being selected from sodium caprolactam).In a specific embodiment, be used in the solution of the sodium caprolactam in caprolactam, such as, from Br ü ggemann, DE's c10 is the sodium caprolactam of 17 to 19 in caprolactam % by weight.Equally especially, suitable catalyst B) be caprolactam magnesium bromide, such as, from Br ü ggemann, DE's c1.
Lactams A) and catalyst B) mol ratio can change in a wide range, but it is generally 1:1 to 10000:1, preferred 5:1 to 1000:1, especially preferably 1:1 to 500:1.
The polymerisable compound used in the present invention comprises the activator C of at least one for anionic polymerisation).
Term activator also comprises the precursor of the N-substituted lactams of the activation of the lactams forming activation together with lactams in position.The quantity of the chain of growth depends on the amount of activator.Usually be suitable as activator C) compound be isocyanates, acid anhydrides and acyl halide, and these materials and lactam monomers reaction product.
Suitable activator C) especially aliphatic diisocyanate, such as two isocyanic acid butylidene esters, two isocyanic acid hexylidene esters, two isocyanic acid Ya Xinji esters, the sub-decyl ester of two isocyanic acids, the sub-undecyl esters of two isocyanic acids, two isocyanic acids sub-dodecyl ester, di-2-ethylhexylphosphine oxide (cyclohexyl-4-isocyanates), IPDIs; Aromatic diisocyanate, such as toluylene diisocya-nate, or di-2-ethylhexylphosphine oxide (phenyl 4-isocyanates), or PIC is (as the isocyanates derived from two isocyanic acid hexylidene esters; hI100/BASF SE) or allophanate (as urea Ethyl formate).Especially, the mixture of the compound mentioned can be used as activator C) use.
Other suitable activator C) be aliphatic diacyl halide, such as succinyl chloride, succinyl bromine, Adipoyl Chloride, adipyl bromine, suberoyl chlorine, suberoyl bromine, sebacoyl chloride, decanedioyl bromine, dodecane diacid chloride, dodecane two acylbromide, 4, 4 '-methylene two (hexamethylene acyl) chlorine, 4, 4 '-methylene two (hexamethylene acyl) bromine, isophorone diacid chloride, isophorone two acylbromide, and aromatics diacyl halide, such as tolyl methylene diacid chloride, tolyl methylene two acylbromide, 4, 4 '-methylene two (phenyl) acyl chlorides, 4, 4 '-methylene two (phenyl) acylbromide.Especially, the mixture of the compound mentioned can be used as activator C) use.
Especially preferred is a kind of polymerisable compound, wherein, as activator C), use at least one to be selected from the compound of aliphatic diisocyanate, aromatic diisocyanate, PIC, aliphatic diacyl halogen and aromatic series diacyl halogen.
In a preferred embodiment, as activator C), use at least one to be selected from the compound of hexamethylene diisocyanate, IPDI, adipyl bromine, Adipoyl Chloride and their mixture as activator C).Especially hexamethylene diisocyanate is preferably used as activator C).
Activator C) can use with the form of solid or solution.Especially, activator C) form in caprolactam of can being dissolved in uses.A suitable activator C) example be 1,6-hexamethylene diisocyanate of caprolactam blocking.A kind of 1,6-hexamethylene diisocyanate of caprolactam blocking is dissolved in the solution of caprolactam can by Br ü ggemann, DE conduct c20 buys.
Lactams A) with activator C) mol ratio can change in a wide range, but it is generally 1: 1 to 10000: 1, preferably 5: 1 to 2000: 1, particularly preferably 20: 1 to 1000: 1.
The polymerisable compound used in the present invention is except above-mentioned composition A), B) and C) except, also comprise the component that at least one is selected from polymer, monomer, filler and/or fibrous material and other additives.
Polymerisable compound can comprise one or more polymer.The optional polymer generated from the polymerization of polymerisable composition in the present invention of polymer in principle, the polymer different from it, and polymeric blends.The polymerisable compound that the present invention uses comprises 0 to 40 % by weight, and preferably 0 to 20 % by weight, the especially preferably at least one polymer of 0 to 10 % by weight, based on the total weight of polymerisable compound.When polymerisable compound comprises at least one polymer, its amount preferably at least 0.1 % by weight, especially preferably 0.5 % by weight, based on the total weight of polymerisable compound.In a specific embodiment, polymerisable compound does not comprise the polymer of the polymerisable compound polymerization formation used in the present invention.In another specific embodiment, polymerisable compound does not comprise polymer.
Polymerisable compound can comprise one or more polymer, and wherein said polymer preferably adds described composition in polymer form.In the first embodiment, the polymer of interpolation contains the group being suitable for forming block and/or graft copolymer together with the polymer formed by lactam monomers.The example of this group is epoxy radicals, amine, carboxyl, acid anhydrides, oxazoline, carbodiimide, carbamate, isocyanates and lactams group.
In another embodiment, polymerisable compound comprises at least one polymer, described polymer is selected from polystyrene, styrol copolymer, polyoxygenated phenylene ether (polyphenylene oxide ethers), polyolefin, polyester, polyethers, polyetheramine, polymer from vinyl monomer, and the mixture of above-mentioned polymer.In a preferred embodiment, polymerisable compound comprises at least one polymer, described polymer is selected from styrene acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene copolymer (ABS), SB (SB), polyethylene (HTPE (high temperature polyethylene), LTPE (low-temperature polyethylene)), polypropylene, poly 1-butene, polytetrafluoroethylene (PTFE), PETG (PET), polyamide, polyethylene glycol (PEG), polypropylene glycol, polyether sulfone (PESU or PES), polyvinyl chloride, polyvinylidene chloride, polystyrene, impact modification polystyrene, PVK, polyvinyl acetate, polyvinyl alcohol, polyisobutene, polybutadiene, polysulfones and their mixture.These materials such as improve the character of product, the compatibility of component and viscosity.
In one embodiment, solid polymerizable composition comprises at least one filler.For object of the present invention, statement " filler " is interpreted as wider scope, comprises granular filler, fibrous material and interim form required arbitrarily.The particle size of granular filler can be very wide scope, from dust to coarse granule.Filler material used can comprise organic or inorganic filler and/or organic or inorganic fibrous material.Such as, inorganic filler can be used, such as kaolin, chalk, wollastonite, talcum powder, calcium carbonate, silicate, titanium dioxide, zinc oxide, graphite, glass particle, such as bead, Nano filling, such as CNT (CNT, carbon black, nanoscale or other phyllosilicates (phyllosilicate), nano aluminium oxide (Al 2o 3), nano titanium oxide (TiO 2), Graphene and nano silicon (SiO 2).
Also one or more fibrous materials can be used.Preferably it is selected from known inorganic reinforcing fiber, such as boron fibre, glass fibre, carbon fiber, silicon dioxide fibre, ceramic fibre and basalt fibre; Organic reinforcing fiber, such as aramid fiber, polyester fiber, nylon fiber, polyethylene fiber peacekeeping natural fiber, such as wood-fibred, flax fiber, hemp and sisal fiber.
Especially glass fibre, carbon fiber, aramid fiber, boron fibre, metallic fiber or potassium titanate fibre is preferably used.Especially short glass fiber is used.The fiber mentioned preferably uses with the form of short fiber in polymerisable compound.The preferred scope of average fiber length of these short fibers is 0.1 to 0.4mm, also can use the fibrous material of the form of long fibre or short fiber and long fibre mixture.But it is favourable for they directly being joined mould support and uses, as hereafter to lay fiber scrim or fibrous braid (fiber braids) as described in.Suitable fiber also comprises the fiber that average fiber length scope is 0.5 to 1mm, and long fibre, and its average fibre length is preferably greater than 1mm, preferably the scope of 1 to 10mm.For the direct suitable fiber used on mould support, there is no the upper limit of length in principle.Such as, the fiber scrim of laying or the fibre length of fibrous braid can be described as unrestrictedly.
Especially described filler and/or the mixture of fibrous material can also be used.Especially preferably use glass fibre and/or glass particle, especially bead as filler and/or fibrous material.
The polymerisable compound used in the present invention preferably includes 25 to 90 % by weight, especially 30 to 80 % by weight at least one filler and/or fibrous material, based on the total weight of polymerisable compound.In a specific embodiment, the polymerisable compound used in the present invention comprises at least one filler and/or the fibrous material of 30 to 50 % by weight, based on the total weight of polymerisable compound.In another specific embodiment, the polymerisable compound used in the present invention comprises at least one filler and/or the fibrous material of 50 to 90 % by weight, based on the total weight of polymerisable compound.
In a preferred embodiment, polymerisable compound can comprise the other additive of at least one.Based on the total weight of polymerisable compound, the amount of additive preferably 0 to 5 % by weight, preferably 0 to 4 % by weight, especially preferably 0 to 3.5 % by weight.The example of the additive that can add can be stabilizing agent, such as mantoquita, dyestuff, antistatic additive, releasing agent, antioxidant, light stabilizer, PVC stabilizer, lubricant, fire retardant, foaming agent, impact modifier, nucleator and its combination.If polymerisable compound comprises at least one additive, then the amount of additive is preferably at least 0.01 % by weight, based on the total weight of polymerisable compound, especially preferably at least 0.1 % by weight, based on the total weight of polymerisable compound, especially at least 0.5 % by weight, based on the total weight of polymerisable compound.
The polymerisable compound used in the present invention preferably includes a kind of impact modifier as additive.If polymerizable compound uses as impact modifier, then it adds up together with above-mentioned polymer.Especially, polydiene polymers (such as polybutadiene, polyisoprene) uses as a kind of impact modifier.Described polydiene polymers preferably includes anhydride group and/or epoxide group.The glass transition temperature of polydiene polymers is especially lower than 0 DEG C, preferably lower than-10 DEG C, especially preferred lower than-20 DEG C.The preparation of polydiene polymers can based on the copolymer of a kind of polydiene and polyacrylate, polyacrylic acid ethyl and/or polysiloxanes, the method (e.g., emulsion polymerisation, suspension polymerization, polymerisation in solution or gas-phase polymerization) known can be used.
The present invention above prepares polyamide molding body by filling a kind of above-mentioned solid-state polymerisable compound to the mould support (rotational molding mould) in rotational molding system.Suitable rotational molding system is that itself is known.
Preferably prepare in the method for polyamide molding body at one, a kind of polymerisable compound as above is filled into mould support, and this mould support first heated before filling polymerisable compound.The polymerisable compound used in the present invention is when filling, and the temperature of preferred mold support is the temperature raised, and this temperature is selected according to used lactams.When using caprolactam as lactam component, the temperature of mould support is preferably 20 to 55 DEG C.
Preferably prepare in the method for polyamide molding body at one, as mentioned above, the furnace chamber that mould support and/or mould support are positioned at is at filling process rear enclosed.It is favourable that make the component not participating in the process the preparing polyamide molding body content of---being specially water, carbon dioxide and/or oxygen---minimizes.Therefore the component used and equipment should substantially not moisture, carbon dioxide and/or oxygen.A kind of inert atmosphere of preferred use for store use component and/or for during being filled into rotational molding equipment and/or between polymerization period.A suitable inert gas example is nitrogen or argon gas.In several cases, there is no need complete deactivation, but container used, mould etc. use the covering of a kind of inert gas just enough.
The present invention is in step c) in prepare polyamide molding body by the temperature increasing mould support, thus make polymerisable compound become flowable liquid.Here the selection of temperature makes it possible to the flowable liquids form producing polymerisable compound, and makes it be evenly distributed on the interior zone of mould support.Mould support method known to those skilled in the art heats.This is preferably in stove, such as, realizes in the heating furnace of normally combustion gas.
Above-mentioned polymerizable compositions is heated to the temperature becoming the liquid with enough mobility, to be distributed in the inside of mould support when rotating.For polymerisable compound is transformed into flowable liquid condition, the fusing point usually it being at least heated to pure lactam component is just enough.In step c) in, the heating of polymerisable compound used in the present invention is preferably higher than the fusing point of lactam component used 1 to 20 DEG C, and especially preferably 3 to 15 DEG C, especially the temperature of 5 to 10 DEG C is carried out.In step c) in, the heating of polymerisable compound used in the present invention is preferably being less than 180 DEG C, is especially preferably less than 160 DEG C, is especially less than 120 DEG C, and the temperature being particularly preferably less than 90 DEG C is carried out.In step c) in, the lactam component selected in polymerisable compound is depended in the selection of temperature.
The present invention is in steps d) in by the polymerizable compositions of above-mentioned flowable liquids state being distributed to the interior zone of mould support equably and preparing polyamide molding body.Flowable liquids composition be uniformly distributed the viscosity depending on polymerisable compound.The impact of its lactam component such as used, activator and catalyst.Can flow composition be uniformly distributed preferably after 1 to 60 minute, especially after 2 to 30 minutes, especially obtained after 3 to 15 minutes.
The polymerisable compound used in preferred the present invention realizes to the dual-axis rotation of the liquid transformation mould support that can flow.The dual-axis rotation of the distribution mould support of the flowed polymerisable compound used in same preferably the present invention realizes.
The present invention is in steps d) in by polymerizing polymerizable composition and prepare polyamide molding body after above-mentioned polymerisable compound has been transformed into flowable liquids and has distributed.
The present invention by be heated to above polymerization temperature temperature and in steps d) in above-mentioned polymerisable compound is polymerized, thus prepare polyamide molding body.Here temperature depends on method parameter.Preferred temperature range is 50 to 200 DEG C.Especially preferable temperature is within the scope of 60 to 170 DEG C.Specifically, use caprolactam as temperature during lactam component within the scope of 85 to 150 DEG C.
Preferably in steps d) in polymerization by increasing the temperature of mould support and carrying out dual-axis rotation to implement.
In one embodiment, polyamide molding body is prepared by being polymerized above-mentioned polymerisable compound and extending the time of staying of flowable liquids polymerisable compound in mould support.
The polymerization time of the polymerisable compound used in the present invention depends on temperature, and the character of catalyst and activator and concentration.Steps d in the inventive method) in the polymerization process of polymerisable compound usually after 1 to 60 minute, preferably complete after 2 to 30 minutes.In the method for the invention, polymerization time is defined as the polymerization temperature (final temperature) that originates in furnace temperature and reach selected and ends to begin to cool down (=step e)) time.
The velocity of rotation of mould support during being transformed into flowable liquids, distributed process and polymerisation depend on the viscosity of polymerisable compound.The rotary speed of axle usually in the scope of 1 to 40rpm (rpm), the preferably scope of 1 to 20rpm.
Usually the enable pollutant causing anionic polymerisation to stop such as water, carbon dioxide and oxygen is minimized is favourable.Therefore all components used all should very dry and oxygen-free and carbon dioxide.Preferred polymeric reaction is implemented when substantially eliminating oxygen, carbon dioxide and water.Especially the step in method of the present invention is implemented when substantially eliminating oxygen, carbon dioxide and water.
Preferably being transformed into liquid, during the distribution of the polymerisable compound that can flow and polymerisation, have inert atmosphere in mould support.Especially, during a kind of inert atmosphere is present in polymerisation.As mentioned above, usually, deactivation is dispensable completely, but the independent step can implementing the inventive method under a kind of inert gas of appropriate amount exists a), b), c) and/or e) or all these steps.
In the present invention, steps d) in rotation under polymerisation after cool the polymeric compositions (=step e) of generation).To this, moulding bodies is cooled to the temperature of polymeric compositions dimensionally stable usually.Step e) in mould support be cooled to preferably 20 to 80 DEG C, especially preferably 30 to 70 DEG C, the particularly preferably temperature of 50 to 70 DEG C.
Cooling is preferably carried out under the dual-axis rotation condition of mould support.Preferably mould support shifted out from furnace chamber and cool.Contact preferably by by mould support with cooling agent such as air or air/water mixture and mould support is cooled, or by opening mould support simply and cooling.Cooling stage depends on the wall thickness of the polyamide molding body of preparation.
Cooling procedure terminates when polyamide molding body dimensionally stable.Moulding bodies can be shifted out from mould support.
The present invention also provides a kind of method for the preparation of above-mentioned polyamide molding body, and wherein mould support comprises at least one filler and/or fibrous material.
In a preferred embodiment, mould support comprises a kind of braided fiber and/or a kind of fiber mesh material.Such as a kind of fiberglass packing and/or fiberglass reticular thing.
Also a kind of filler and/or fibrous material can be loaded in mould support together with polymerisable compound.The filler optionally added and/or fibrous material can be selected from above-mentioned filler and/or fibrous material.
By the inventive method, the polyamide molding body with high levels of filler and/or fibrous material can be prepared.Especially, in the polyamide molding body prepared by method of the present invention, the content range of filler and/or fibrous material is 30 to 90 % by weight, especially 30 to 80 % by weight, preferably 30 to 50 % by weight, and based on the total weight of polymerisable compound.In a specific embodiment, in polyamide molding body, the content of filler and/or fibrous material is 50 to 90 % by weight, based on the total weight of polymerisable compound.
The polyamide molding body prepared by method of the present invention especially can as the material for the preparation of car body part, as compartment or felloe thing (wheel surround), or automobile component, such as vehicle frame covering (frame cladding) or instrument board, and for interior.Other possibility purposes of polyamide molding body are the liners as groove (tanks), gear, shell, packing film and coating.
In principle, the polyamide molding body prepared by method of the present invention is applicable to the small electric apparatus of any family expenses, such as mobile phone, notebook computer, iPad or the common plastics goods for simulating metal.
For being used polymerisable compound to be compared by method and the use melt or the method for polymer powder that polyamide molding body is prepared in the reaction of activated anionic implementing anionic lactam polymerisation as raw material by rotomolding processes, there is a lot of advantages in the present invention.
For being used polymerisable compound to prepare the method for polyamide molding body and use melt ratio as raw material by the reaction of activated anionic implementing anionic lactam polymerisation by rotomolding processes in the present invention, in auxiliary operation, there is advantage, such as, raw material is easy to store, raw material is easy to transport, and is easy to raw material to introduce in operation.
In the present invention for being used polymerisable compound to react by activated anionic implementing anionic lactam polymerisation the advantage that the method for preparing polyamide molding body also has as raw material by rotomolding processes be, polymerisable compound has lower fusing point, therefore rotomoulding is compared with use polymer powder, needs less time and lower energy.
In the present invention for being used polymerisable compound to react by activated anionic implementing anionic lactam polymerisation the advantage that the method for preparing polyamide molding body also has as raw material by rotomolding processes be, flowable liquids polymerisable compound has lower viscosity, therefore compare with polymer powder, demonstrate good mobility, obviously better evenly and distribute faster in mould support.
That polymer is original position generation for being used polymerisable compound react by activated anionic implementing anionic lactam polymerisation the advantage that the method for preparing polyamide molding body also has as raw material by rotomolding processes in the present invention.Therefore polyamide molding body can solidify quickly than polymer powder, especially when temperature is lower than polyamide fusing point.
In the present invention for being used polymerisable compound to react by activated anionic implementing anionic lactam polymerisation the advantage that the method for preparing polyamide molding body also has as raw material by rotomolding processes be, solid-state polymerisable compound is added in mould support (rotational molding mould), in a mold, flowable liquid, distribution and polymerization can be transformed into, thus obtain polyamide molding body.
In the present invention for being used polymerisable compound to react by activated anionic implementing anionic lactam polymerisation the advantage that the method for preparing polyamide molding body also has as raw material by rotomolding processes be, compared to the prior art, rotomoulding heating period (polymerisable compound is transformed into flowable liquids and distributes) that can shorten and the cooling stage that shortens are implemented.
For being used polymerisable compound to react by activated anionic implementing anionic lactam polymerisation the high efficiency that the method preparing polyamide molding body has energy and time as raw material by rotomolding processes in the present invention.
The following examples further illustrate the present invention.Described embodiment describes aspects more of the present invention, but should not think limiting the scope of the invention.
Embodiment
Preparation 150L liquid container:
Preheat the mould support of deactivation to temperature T mould.Powdery polymerisable compound A is encased in mould support by the solids valve of deactivation.At T stove, 1furnace temperature, mould support with rotary speed x around main shaft (primary axis) rotate, and with rotary speed y around secondary axes (secondary axis) rotate, rotational time t 1.Furnace temperature is risen to T stove, 2.In heating process and reaching target temperature T stove, 2after, the rotation of mould support continues time t in the same way 2.Once close the energy supply of stove, the method B cooling of mould support, at time t 3after open.Shift out the liquid container made
c20=N, N '-hexa-methylene two (carbamoyl-epsilon-caprolactams)
the sodium caprolactam of the 17-19% in C10=caprolactam
c1=caprolactam magnesium bromide

Claims (14)

1. prepare a method for polyamide molding body, wherein
A () provides a kind of polymerisable compound, comprise
A) at least one lactams,
B) at least one catalyst, and
C) at least one activator, be selected from isocyanates, acid anhydrides, acyl halide, these materials with
A) product, and their mixture,
(b) by step a) in the polymerisable compound that provides can load in the mould support of rotational molding system by liquid form with solid-state,
C () under rotation, the polymerisable compound in heating mould support becomes the temperature of flowable liquids to polymerisable compound, and flowable liquids polymerisable compound is evenly distributed,
D () makes polymerisable compound be polymerized under rotation,
The composition of (e) cooling polymerization, and
F polyamide molding body shifts out by () from mould support.
2. method according to claim 1, wherein polymerisable compound is the form of particle, and wherein all particles have identical composition substantially, and particle includes component A), B) and C).
3. according to the method for aforementioned any one of claim, wherein when polymerisable compound is in step b) in when being loaded into, the temperature of mould support is 20 to 55 DEG C.
4. according to the method for aforementioned any one of claim, wherein in step c) in, polymerisable compound is heated to higher 1 to 20 DEG C than used lactams fusing point, preferably 3 to 15 DEG C, the especially preferably temperature of 5 to 10 DEG C.
5. method according to claim 4, wherein step c) carrying out 1 to 60 minute, preferably 2 to 30 minutes, especially preferably terminate after 3 to 15 minutes.
6. according to the method for aforementioned any one of claim, wherein in steps d) in, polymerisable compound is heated to higher 10 to 100 DEG C than used lactams fusing point, preferably the temperature of 30 to 80 DEG C.
7. method according to claim 6, wherein steps d) carrying out 1 to 60 minute, preferably terminate after 2 to 30 minutes.
8. according to the method for aforementioned any one of claim, wherein in step e) in, mould support is cooled to 20 to 80 DEG C, preferably 30 to 70 DEG C, especially preferably the temperature of 50 to 70 DEG C.
9. according to the method for aforementioned any one of claim, wherein, based on the total weight of composition, polymerisable compound comprises:
At least one lactams A of 50 to 99.7 weight portions),
At least one catalyst B of 0.1 to 3.6 weight portion), and
At least one activator C of 0.2 to 8.0 weight portion).
10. according to the method for aforementioned any one of claim, wherein polymerisable compound comprises the lactams A that at least one is selected from following substances): epsilon-caprolactams, 2-piperidones, 2-Pyrrolidone, spicy inner formyl amine, oenantholcatam, lauric lactam, and their mixture.
11. according to the method for aforementioned any one of claim, wherein polymerisable compound comprises at least one catalyst B), be selected from sodium caprolactam, caprolactam potassium, caprolactam magnesium bromide, caprolactam magnesium chloride, dicaprolactam magnesium, sodium hydride, sodium, NaOH, sodium methoxide, caustic alcohol, sodium propoxide, sodium butoxide, hydrofining, potassium, potassium hydroxide, potassium methoxide, potassium ethoxide, potassium propoxide, butanols potassium and their mixture.
12. according to the method for aforementioned any one of claim, and wherein polymerisable compound comprises the activator c that at least one is selected from following substances): hexamethylene diisocyanate, IPDI, adipyl bromine, Adipoyl Chloride and their mixture.
13. according to the method for aforementioned any one of claim, and wherein polymerisable compound is the form of particle, and the scope of average diameter is 1 to 2000 μm, preferably 10 to 1000 μm, especially preferably 50 to 500 μm, very especially preferably 100 to 200 μm.
What define any one of 14. claims 1 to 13 comprises composition A), B) and polymerisable compound C) be used for the purposes being prepared polyamide molding body by the method for rotational molding.
CN201380017044.9A 2012-03-27 2013-03-26 Method for producing polyamide molded bodies from a polymerizable composition by means of a rotational molding process Pending CN104245268A (en)

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