CN1910213A - Polyformals and copolyformals as hydrolysis protection layers on polycarbonates - Google Patents

Polyformals and copolyformals as hydrolysis protection layers on polycarbonates Download PDF

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Publication number
CN1910213A
CN1910213A CNA200580002585XA CN200580002585A CN1910213A CN 1910213 A CN1910213 A CN 1910213A CN A200580002585X A CNA200580002585X A CN A200580002585XA CN 200580002585 A CN200580002585 A CN 200580002585A CN 1910213 A CN1910213 A CN 1910213A
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hydroxyphenyl
polycarbonate
preferred
polyformal
group
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Chinese (zh)
Inventor
H·W·霍伊尔
R·韦尔曼
R·胡芬
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Covestro Deutschland AG
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Bayer MaterialScience AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D159/00—Coating compositions based on polyacetals; Coating compositions based on derivatives of polyacetals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/60—Bottles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2459/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Polyethers (AREA)
  • Paints Or Removers (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Wrappers (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to a hydrolysis-resistant multilayer product comprising at least one layer comprising a thermoplastic material and at least one layer comprising at least one polyformal or copolyformal. The invention further relates to compositions containing polyformals or copolyformals and possible additives and to the use of polyformals or copolyformals for producing a hydrolysis-resistant layer.

Description

Polyformal and copolymerization formal as the hydrolysising protection layer on the polycarbonate
The present invention relates to comprise one deck at least of containing thermoplastics and contain the multilayer product of anti-hydrolysis of one deck at least of at least a polyformal or copolymerization formal, sheet material especially, film, container is water bottle for example, infant bottle or medical product.The invention still further relates to the composition that contains polyformal or copolymerization formal and possible additive and polyformal and/or copolymerization formal and be used to prepare the purposes of hydrolysising protection layer.
The invention still further relates to this multilayer product of preparation, for example sheet material, medical product or various container, for example bottle product, infant bottle, water bottle and the method that contains the other products of described sheet material.
Solid or multi-layer sheet for example is coated with UV coextrusion layer in the outside of one or both sides usually, is damaged (for example yellowing) by ultraviolet ray to prevent them.Yet other multilayer product also prevents ultraviolet infringement in the same way.On the contrary, the use heat plastic material is not described in the prior art as providing anti-hydrolysis to destroy the layer of provide protection.
Below summed up and the relevant prior art of multilayer protection product:
EP-A 0 110 221 discloses the sheet material that comprises two-layer polycarbonate, and wherein one deck contains the UV light absorber of 3wt% at least.These sheet materials can be by producing according to the coextrusion of EP-A 0 110 221.
EP-A 0 320 632 discloses and has comprised the two layers of thermoplastic polymkeric substance, the moulded product of optimization polycarbonate, and wherein one deck contains the benzotriazole of special replacement as UV light absorber.EP-A 0,320 632 also discloses the method for preparing these moulded products by coextrusion.
EP-A 0 247 480 discloses multi-layer sheet, wherein except a kind of sheet material by the thermoplastic polymer preparation, also have a kind of sheet material by the branching polycarbonate preparation, described sheet material by polycarbonate contains the benzotriazole of special replacement as UV light absorber.The method for preparing these sheet materials by coextrusion is disclosed equally.
EP-A 0 500 496 discloses with special triazine stable with the polymer composition that prevents action of ultraviolet ray and they are as the outer field purposes in the multilayer system.Polycarbonate, polyester, polymeric amide, polyacetal, polyphenylene oxide and polyphenylene sulfide are enumerated as polymkeric substance.
According to prior art, water bottle, for example 5 gallon bottles do not have multilayered structure (DE19943642, DE 19943643, EP-A 0411433).The feeding bottle that can re-use or the situation of infant bottle are like this equally.
Polycarbonate container for example prepares by extrusion-blown modling or injection blow molding.
In extrusion-blown modling, particle is used the single screw extrusion machine fusion usually, by the die head molding, forms the parison of supporting oneself, and seals with blow mold then, and this blow mold is clamped together this parison in the lower end.At mould inside, parison swell is to give this parison desired shape.After cooling stage, open mould, can take out blow-molded article and (for example be described in greater detail in Brinkschr  der, F.J. " Polycarbonate " in Becker, Braun, Kunststoff-Handbuch, the 3/1st volume, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag, Munich, in Vienna 1992, the 257-264 pages or leaves).
For extrusion-blown modling, advantageously use height pseudo-plasticity polycarbonate, so that obtain high melt stability.Branching polycarbonate is especially pseudoplastic.
Injection blow molding is the combination of injection moulding and blowing.
This method is undertaken by three steps:
1) parison injection moulding in the plasticity range of polycarbonate
2) parison in the thermoplasticity scope of polycarbonate, expand (core of injection mold also is the air blowing plug)
3) take out blow-molded article, optional with the air cooling plug of blowing.
(this method is described in greater detail in Anders, S., Kaminski, A., Kappenstein, R., " Polycarbonate " in Becker/Braun, Kunststoff-Handbuch, the 3/1st volume, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl HanserVerlag, Munich, in Vienna 1992, the 223-225 pages or leaves).
Yet the product of learning from prior art does not have a kind of all obtaining gratifying result aspect each, especially with regard to the permanent stability of hydrolysis.More than 60 ℃, water destruct polycarbonate.Contact for a long time with boiling water and to cause molecular weight to lower, this thermo-stabilizer for example organophosphite in the presence of further quicken.In addition, preferably basic hydrolysis of polycarbonate.Microwave radiation has further been quickened this degraded.
In prior art patent, do not mention the hydrolysising protection layer and overcome this shortcoming.
From prior art, therefore, purpose provides multi-layer product or coating container for example water bottle or medical product, described product can be sterilized in superheated vapour, compared with prior art shown improved performance, for example for the improvement permanent stability of the hydrolysis in water (even at high temperature) and in the bronsted lowry acids and bases bronsted lowry environment.
This purpose becomes basis of the present invention.
This purpose obtains as the coating of polymer base by containing some polyformal or copolymerization formal astoundingly.
Coating based on the product of polyformal or copolymerization formal has shown wonderful superiority compared with prior art, and this is with regard to the obviously higher hydrolytic resistance of comparing with polycarbonate.
This is wonderful especially, because polyformal can be considered to complete acetal, according to the common viewpoint that those skilled in the art held, it should show the high susceptibility to hydrolysis, at least in acid environment.Yet, on the contrary, though by the coating of polyformal preparation for acid solution and even also can hydrolysis under comparatively high temps.
Therefore the application provides the coating that contains following general formula (1a) or polyformal (1b) or copolymerization formal:
Wherein group O-D-O and O-E-O represent any diphenol foundation group (Diphenolatreste), wherein-D-and-E-has 6-40 C atom, the aromatic group of preferred 6-21 C atom, described group can contain one or more aromatics or fused aromatic nuclear, this nuclear is optional to contain heteroatoms, and described group is optional by C 1-C 12Alkyl or halogen replace and can contain aliphatic group, cycloaliphatic groups, and aromatic kernel or heteroatoms are as connecting base (Br ü ckenglieder), wherein k represents 1-1500, preferred 2-1000, especially preferred 2-700, the integer of the most preferred 5-500 and preferred especially 5-300, o represents 1-1500, preferred 1-1000, especially preferred 1-700, the numerical value of the most preferred 1-500 and preferred especially 1-300, and m represents that mark z/o and n represent mark (o-z)/o, and wherein z represents the numerical value of 0-o.
Preferred structure unit according to polyformal of the present invention and copolymerization formal derives by having with following formula (2a), (2b), (2c) and general formula (2d):
Figure A20058000258500052
Figure A20058000258500061
Basic diphenol foundation group, wherein R described in its bracket 1And R 2Represent H independently of one another, linearity or branching C 1-C 18Alkyl or alkoxyl group, halogen be Cl or Br for example, or the optional aryl or aralkyl that replaces of expression, preferably represents H or linearity or branching C 1-C 12Alkyl is especially preferably represented H or C 1-C 8Alkyl is especially the most preferably represented H or methyl,
X represents singly-bound, can be by C 1-C 6Alkyl, the C that preferable methyl or ethyl replace 1-C 6Alkylidene group, C 2-C 5Alkylidene (Alkyliden), C 5-C 6The ring alkylidene, or choose wantonly and can contain heteroatomic aromatic ring condensed C with other 6-C 12Arylidene, wherein p represents 1-1500, preferred 2-1000, especially preferred 2-700, the integer of the most preferred 5-500, particularly 5-300, p represents 1-1500, preferred 1-1000, especially preferred 1-700, the most preferred 1-500, the numerical value of preferred especially 1-300, and q represents that mark z/p and r represent mark (p-z)/p, and wherein z represents the numerical value of 0-p, group-O-D-O-and-part of O-E-O-also represents independently of one another by one or more trifunctional compound deutero-groups, like this, the 3rd combining site has appearred in this, that is, and and the branch of polymer chain.
Therefore polyformal or copolymerization formal can be linearity or branching.
The diphenol foundation group of formula (1) and (2) is especially preferably derived by the bis-phenol of enumerating below being fit to:
Quinhydrones, Resorcinol, dihydroxybiphenyl, two (hydroxyphenyl) paraffinic hydrocarbons, two (hydroxyphenyl) naphthenic hydrocarbon, two (hydroxyphenyl) thioether, two (hydroxyphenyl) ether, two (hydroxyphenyl) ketone, two (hydroxyphenyl) sulfone, two (hydroxyphenyl) sulfoxide, α, α '-two (hydroxyphenyl) diisopropyl benzene, and their cycloalkylation and ring halogenated compound, also have α, ω-two (hydroxyphenyl) polysiloxane is enumerated as the example of the bis-phenol under general formula (1).
Preferred bis-phenol for example is 4,4 '-dihydroxybiphenyl (DOD), 4,4 '-dihydroxybiphenyl ether (DOD ether), 2,2-pair-(4-hydroxyphenyl) propane (dihydroxyphenyl propane), 1,1-pair-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (bis-phenol TMC), 1,1-pair-(4-hydroxyphenyl) hexanaphthene, 2,4-pair-(4-hydroxyphenyl)-2-methylbutane, 1,1-pair-(4-hydroxyphenyl)-1-diphenylphosphino ethane, 1,4-pair-[2-(4-hydroxyphenyl)-2-propyl group] benzene, 1,3-pair-[2-(4-hydroxyphenyl)-2-propyl group] benzene (bis-phenol M), 2,2-pair-(3-methyl-4-hydroxyphenyl) propane, 2,2-pair-(3-chloro-4-hydroxyphenyl) propane, two-(3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-pair-(3,5-dimethyl-4-hydroxyphenyl) propane, two-(3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-two-(3,5-dimethyl-4-hydroxyphenyl)-the 2-methylbutane, 2,2-pair-(3,5-two chloro-4-hydroxyphenyl) propane and 2, two (3, the 5-two bromo-4-hydroxyphenyl) propane of 2-.
Particularly preferred bis-phenol for example is 2,2-pair-(4-hydroxyphenyl) propane (dihydroxyphenyl propane), and 4,4 '-dihydroxybiphenyl (DOD), 4,4 '-dihydroxybiphenyl ether (DOD ether), 1,3-pair-[2-(4-hydroxyphenyl)-2-propyl group] benzene (bis-phenol M), 2,2-pair-(3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-pair-(4-hydroxyphenyl)-1-diphenylphosphino ethane, 2,2-two-(3,5-two chloro-4-hydroxyphenyl) propane, 2, two (3, the 5-two bromo-4-hydroxyphenyl) propane of 2-, 1,1-pair-(4-hydroxyphenyl) hexanaphthene and 1,1-pair-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (bis-phenol TMC).
More specifically preferably 2,2-pair-(4-hydroxyphenyl) propane (dihydroxyphenyl propane), 4,4 '-dihydroxybiphenyl (DOD), 4,4 '-dihydroxybiphenyl ether (DOD ether), 1,3-pair-[2-(4-hydroxyphenyl)-2-propyl group] benzene (bis-phenol M) and 1,1-pair-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (bis-phenol TMC).
The most especially preferred is 2,2-pair-(4-hydroxyphenyl) propane (dihydroxyphenyl propane) and 1, and 1-pair-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (bis-phenol TMC).
These bis-phenols can be separately and the use that be mixed with each other; Comprise equal polyformal and copolymerization formal.These bis-phenols learn from document, perhaps can produce by the method for from document, learning (for example referring to people such as H.J.Buysch, Ullmann ' s Encyclopedia of IndustrialChemistry, VCH, New York 1991, the 5 editions, the 19th volume, the 348th page).
Can come branching with controllable manner by using a spot of trifunctional compound that is called branching agent consciously according to polyformal of the present invention.Some branching agents that are fit to are: Phloroglucinol, 4,6-dimethyl-2,4,6-three-(4-hydroxyphenyl) heptene-2; 4,6-dimethyl-2,4,6-three-(4-hydroxyphenyl) heptane; 1,3,5-three-(4-hydroxyphenyl) benzene; 1,1,1-three-(4-hydroxyphenyl) ethane; Three-(4-hydroxyphenyl) phenylmethanes; 2,2-pair-[4,4-pair-(4-hydroxyphenyl) cyclohexyl] propane; 2,4-pair-(4-hydroxyphenyl sec.-propyl) phenol; 2,6-pair-(2-hydroxyl-5 '-methyl-benzyl)-4-methylphenol; 2-(4-hydroxyphenyl)-2-(2, the 4-dihydroxy phenyl) propane; Six-(4-(4-hydroxyphenyl sec.-propyl) phenyl) adjacency pair phthalic acid esters; Four-(4-hydroxyphenyl) methane; Four-(4-(4-hydroxyphenyl sec.-propyl) phenoxy group) methane; α, α, α "-three-(4-hydroxyphenyl)-1,3, the 5-triisopropylbenzene; 2, the 4-resorcylic acid; Trimesic acid; Cyanuric chloride; 3,3-pair-(3-methyl-4-hydroxyphenyl)-2-oxo-2, the 3-indoline; 1,4-is two-(4 ', 4 "-dihydroxyl triphenyl) methyl) benzene and especially: 1,1,1-three-(4-hydroxyphenyl) ethane and pair-(3-methyl-4-hydroxyphenyl)-2-oxo-2, the 3-indoline.
The use of this branching agent has been obtained the derivative of corresponding chemical formula (1) and (2) by its idealized structure.This means,, formed to have and derived and the structural unit of three combining units coming that depend on employed branching agent, described combining unit can also be as formation such as ester functional groups by employed branching agent according to the consumption of branching agent.
In employed diphenol is benchmark, and the mixture that can choose shared branching agent or branching agent wantonly of 0.05-2mol% can add with diphenol, but also can add in the stage afterwards at synthetic.
Phenol is phenol for example, and alkylphenol is cresols and 4-tert.-butyl phenol for example, chlorophenol, bromine phenol, cumyl phenol or their mixture are preferably with 1-20mol%, and the amount of the bis-phenol of preferred 2-10mol%/mol is as the chain terminator of polyformal, and this polyformal is as the raw material in the coextrusion coating.Phenol, 4-tert.-butyl phenol or cumyl phenol are preferred.
Have formula (1a) and (1b) or polyformal (2a-d) and copolymerization formal for example prepare by solution methods, be characterised in that bis-phenol and chain terminator and methylene dichloride or α, α-toluene dichloride is at methylene dichloride or α, α-toluene dichloride and the high boiling solvent that is fit to be N-Methyl pyrrolidone (NMP) for example, dimethyl formamide (DMF), methyl-sulphoxide (DMSO), N-methyl caprolactam (NMC), chlorobenzene, dichlorobenzene, in the homogeneous solution of trichlorobenzene or tetrahydrofuran (THF) (THF), at alkali, under the existence of preferred sodium hydroxide or potassium hydroxide, under 30-160 ℃ temperature, react.Preferred high boiling solvent is NMP, DMF, DMSO and NMC, especially preferred NMP, NMC, DMSO and the most preferred NMP and NMC.This reaction can also be undertaken by several stages.The optional ring-type separate impurities that needs after the neutrality washing of organic phase by intermediate processing or by crude product and the solvent that dissolves described ring compound for example the classification compounding of acetone carry out.Ring-type impurity is dissolved in this solvent basically fully, and can and change this solvent and almost completely be separated by compounding in batches (Kneten).After compounding, use for example about 10 liters acetone (it can be for example polyformal in) can obtain to be starkly lower than the content of 1% ring compound by 5 parts of amounts that join about 6kg.
Can also isolate ring-type polyformal and copolymerization formal by the intermediate processing in the solvent that is fit to, described solvent is as the precipitation agent of required polymkeric substance and the solvent of undesirable ring compound.They are alcohol or ketone preferably.
The temperature of reaction of polycondensation is 30-160 ℃, preferred 40-100 ℃, and especially preferred 50-80 ℃, the most preferred 60-80 ℃.
Therefore the present invention provides described polyformal and copolymerization formal to be used to produce multilayer product, the purposes of coextrusion thing such as multi-layer sheet for example, these multi-layer sheets itself and prepare the method for these multi-layer sheets and the method for compositions that is fit to that coating contains these polyformals or copolymerization formal by coextrusion.
The present invention also provides the product that contains described multi-layer sheet or based on other coated product of polyformal.This product that for example contains described multi-layer sheet or coating itself preferentially is selected from infant bottle, water bottle or the medical product that can sterilize in superheated vapour.
Multilayer product according to the present invention has many advantages.Especially, it has advantage, promptly by the hydrolysising protection layer based on poly-methylal, has obtained permanent stability, especially the obvious improvement of the stability to hydrolysis for aqueous medium.And the easy to manufacture and cost of this sheet material is low, and all starting raw materials can obtain, and are cheap.In addition, in multilayer product according to the present invention, other advantageous property of polycarbonate, for example its good optical and mechanical property are impaired or not or only not obviously.
Multilayer product according to the present invention has other advantage compared with prior art.According to multilayer product of the present invention, for example bottle for example can be produced by coextrusion blowing.This has caused and the advantage of comparing by the product of coating production.For example, in coextrusion, do not have as existing solvent evaporation under the situation of coating system.
In addition, coating has limited storage power.Coextrusion is this shortcoming not.
In addition, coating needs complicated technology.For example, they need blast protection device (if with an organic solvent), the recirculation of solvent and therefore expensive facility investment.Coextrusion is this shortcoming not.
Embodiment preferred of the present invention is described multi-layer sheet or various types of bottle, wherein bottom is made up of the blend and/or the polymethylmethacrylate of polycarbonate and/or Copolycarbonate and/or polyester and/or copolyesters and/or polyestercarbonate and/or polymethylmethacrylate and/or polyacrylic ester and/or polycarbonate and polyester, and the coextrusion layer is made up of the blend of polyformal or copolymerization formal or they and (being total to) polycarbonate and/or (being total to) polyester.
According to the present invention, the hydrolysising protection layer thickness is the 1-5000 micron, preferred 5-2500 micron, and the multilayer product of the most preferred 10-500 micron is preferred.
These sheet materials can be solid sheet, multi-layer sheet, double layer sheet, three-layer tablet material, four synusia materials etc.Multi-layer sheet can also have various sections, for example X section or XX section.Multi-layer sheet can be the corrugated multilayer sheet material in addition.
The double layer sheet that the preferred embodiments of the invention are made up of the hydrolysising protection layer of one deck polycarbonate and one deck polyformal or copolymerization formal or polycarbonate-polyformal blend.
The three-layer tablet material that another embodiment preferred of the present invention is made up of as the hydrolysising protection layer of stratum basale and two superimposed one deck polycarbonate; wherein said two-layer hydrolysising protection layer is identical or different, is made up of polyformal or copolymerization formal or polycarbonate-polyformal blend.
Same preferably as one embodiment of the invention be various types of containers, bottle for example is as water bottle (5 gallon bottle), infant bottle or reusable feeding bottle.
Container on meaning of the present invention can be used for packing, storage or transport liquid, solid or gas.Be used to pack, the container of storage or transport liquid is preferred (fluid container), be used to pack, the container (water bottle) of storage or transport of water is particularly preferred.
Container on meaning of the present invention is that volume is preferably 0.1-50L, the blow-molded container of preferred 0.5-50L, and wherein the volume of 1L, 5L, 12L and 20L is the most especially preferred.
The water bottle of volume 3-5 gallon is the most especially preferred.
The bare weight of container is preferably 0.1-3000g, more preferably 50-2000g, especially preferably 650-900g.
The thick 0.5-5mm that is preferably of wall of a container, more preferably 0.8-4mm.
Container on meaning of the present invention has preferred 5-2000mm, the length of especially preferred 100-1000mm.
These containers have preferred 10-250mm, more preferably 50-150mm, the most preferably maximum perimeter of 70-90mm.
Container on meaning of the present invention preferably has length and is preferably 1-500mm, more preferably 10-250mm, especially preferably 50-100mm, the most preferably bottleneck of 70-80mm.
The wall thickness of the bottleneck of container is preferably 0.5-10mm, especially preferred 1-10mm, the most preferred 5-7mm.
The diameter of bottleneck is preferably 5-200mm.10-100mm is especially preferred, and 45-75mm is the most especially preferred.
The bottle end according to container of the present invention has preferred 10-250mm, more preferably 50-150mm, the most preferably diameter of 70-90mm.
Container on meaning of the present invention can have any geometrical shape, and they for example can be circular, oval or have the polygon on 3-12 bar limit for example or dihedral is arranged.Circle, oval and sexangle are preferred.
The design of container can be based on any surface tissue.Surface tissue preferably level and smooth or ribbed.Can also show several different surface tissues according to container of the present invention.Rib or bead can be around the circumference of container.Their can be separated by any distance or several different distance of can being separated by.Surface tissue according to container of the present invention can show roughening or integrated structure, symbol, ornament, handle coating, company's theory, trade mark, cypher word, manufacturer's explanation, material explanation and/or volume information.
Can have the handle of arbitrary number according to container of the present invention, handle can be positioned at side, top or bottom.These handles can be outside, perhaps can be incorporated in the profile of container.These handles can fold or be fixing.These handles can have arbitrary shape, for example oval, circle or polygon.The length of handle is 0.1-180mm preferably, preferred 20-120mm.
Except polycarbonate according to the present invention, can also contain a spot of other material according to container of the present invention, for example sealing of making by rubber or the handle of making by other material.
Preferably prepare according to container of the present invention by extrusion-blown modling method or injection blow molding method.
In a preferred embodiment that is used for preparing according to the method for container of the present invention, according to polycarbonate according to the present invention with having level and smooth or trough of belt, the forcing machine processing of preferred level and smooth intake zone.
Select the driving power of forcing machine according to screw diameter.For example, for the screw diameter of 60mm, the driving power of forcing machine is about 30-40kW, and for the screw diameter of 90mm, driving power is about 60-70kW.
Normally used general three sections screw rods are fit in the processing of engineered thermoplastic material.
In order to produce the container of volume 1L, the screw diameter of 50-60mm is preferred.In order to produce the container of volume 20L, the screw diameter of 70-100mm is preferred.The length of screw rod preferably screw diameter 20-25 doubly.
Under the situation of blowing, blow mold preferably is heated to 50-90 ℃, to obtain the high-quality vessel surface of flash of light.
In order to ensure the evenly and effectively heating of blow mold, basal region and jacked region can heat separately.
Blow mold preferably seals with the force of compression that compresses welding bead length (Quetschnahtl  nge) of 1000-1500N/cm.
In first being processed, preferably carry out drying according to polycarbonate of the present invention, make the optical quality of container do not degraded with the hydrolysis in the not processed process of polycarbonate by striped or bubble infringement.Dried residual moisture content preferably is lower than 0.01wt%.120 ℃ drying temperature is preferred.Lower temperature can not guarantee sufficient drying, and under higher temperature, has the coherent risk of polycarbonate pellets, so no longer can be processed.The dry air moisture eliminator is preferred.
According to the preferred molten temperature in the course of processing of polycarbonate of the present invention is 230-300 ℃.
Can be used for packing, storage or transport liquid, solid or gas according to container of the present invention.As be used for for example packing, the embodiment of the container of storage or transport liquid is preferred.As can for example be used to pack, the embodiment of the water bottle of storage or transport of water is particularly preferred.
The preferred embodiments of the invention are a kind of like this embodiments, wherein be characterised in that by the container of branching polycarbonate preparation branching polycarbonate contains THPE and/or IBC as branching agent, phenol or alkylphenol are water bottles as chain terminator and the container in the preparation of branching polycarbonate.
A particularly preferred embodiment of the present invention is a kind of like this embodiment, wherein be characterised in that by the container of branching polycarbonate preparation branching polycarbonate contains THPE and/or IBC as branching agent, use phenol in the preparation of branching polycarbonate, polycarbonate is at 260 ℃ and 10s -1Shearing rate under have the melt viscosity of 5500-7000Pas, at 260 ℃ and 1000s -1Shearing rate under have the melt viscosity of 900-1100Pas, and have＜MFR (melt flow index is measured according to ISO 1133) of 3.5g/10min, and this container is a water bottle.
In a particular, described multilayer product is transparent.
Can contain additive according to base material in the multi-layer moldings of the present invention and hydrolysising protection layer.
Depend on Application Areas, the hydrolysising protection layer especially can contain ultra-violet stabilizer or releasing agent.
Described layer can also contain other common process auxiliary agent, especially releasing agent and flow control agent and the stablizer that is generally used for polycarbonate, ultra-violet stabilizer especially, thermo-stabilizer and tinting material and white dyes and mineral dye.
Layer by all known polycarbonate is suitable as the extra play that also has except polyformal and copolymerization formal layer, especially as the stratum basale according to multilayer product of the present invention.
The polycarbonate that is fit to for example is a homo-polycarbonate, Copolycarbonate and thermoplastic polyester carbonic ether.
They preferably have 18,000-40,000, preferred 26,000-36,000, especially 28,000-35,000 weight-average molecular weight Mw, described Mw by in methylene dichloride or with scattering of light calibration etc. measure relative solution viscosity in the mixture of phenol/orthodichlorobenzene of weight and measure.
Production as for polycarbonate, for example with reference to " Schnell; Chemistry and Physicsof Polycarbonate; Polymer Reviews; the 9th volume; Interscience Publishers; New York, London, Sydney 1964 ", " D.C.PREVORSEK, B.T.DEBONA and Y.KESTEN, Corporate Research Center, Allied ChemicalCorporation, Moristown, New Jersey 07960, ' Synthesis of Poly (ester) carbonate Copolymer ', Journal of Polymer Science, Polymer ChemistryEdition, the 19th volume, 75-90 (1980) ", " D.Freitag, U.Grigo, P.R.M ü ller, N.Nouvertne, BAYER AG, ' Polycarbontes ', Encyclopedia of PolymerScience and Engineering, the 11st volume, second edition, 1988, the 648-718 page or leaf " and " Dres.U.Grigo, K.Kircher and P.R.M ü ller ' Polycarbonate ', Becker/Braun, Kunststoff-Handbuch, the 3/1st volume, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, the 117-299 pages or leaves ".
Preferably produce polycarbonate, below use the phase interface polycondensation method to describe as an example by phase interface polycondensation method or melt transesterification method.
The compound that is preferably used as initial compounds is the bis-phenol with following general formula:
HO-Z-OH
Wherein Z is the divalent organic group that has 6-30 carbon atom and contain one or more aromatic groups.
This type of examples for compounds is to belong to dihydroxybiphenyl class, two (hydroxyphenyl) paraffinic, indane bisphenols, two (hydroxyphenyl) ethers, two (hydroxyphenyl) sulfone class, two (hydroxyphenyl) ketone and α, the bisphenols of the group of α '-two (hydroxyphenyl) diisopropyl benzene.
The especially preferred bis-phenol that belongs to the compound group of before having enumerated is a dihydroxyphenyl propane, the tetraalkyl dihydroxyphenyl propane, 1,3-pair-[2-(4-hydroxyphenyl)-2-propyl group] benzene (bis-phenol M), 1, two [2-(4-the hydroxyphenyl)-2-propyl group] benzene of 1-, 1,1-is two-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (BP-TMC) and their mixture of choosing wantonly.
Bisphenol cpd used according to the invention preferably with carbonate compound, phosgene reaction especially is perhaps under the situation of melt transesterification method, with diphenyl carbonate or dimethyl carbonate.
Polyestercarbonate preferably obtains by allowing the bisphenols of before having enumerated, at least a aromatic dicarboxylic acid and optional carbonic acid coordinator react.The example of the aromatic dicarboxylic acid that is fit to is a phthalic acid, terephthalic acid, and m-phthalic acid, 3,3 '-or 4,4'-diphenyldicarboxylic acids and benzophenone dicarboxylic acid.The part of the carbonate group in the polycarbonate, 80mol% at the most, preferred 20-50mol% can be replaced by the aromatic dicarboxylic acid ester group.
The example that is used for the inert organic solvents of phase interface polycondensation method is a methylene dichloride, various ethylene dichloride and chloropropane compound, and tetrachloromethane, trichloromethane, chlorobenzene and toluene(mono)chloride preferably use the mixture of chlorobenzene or methylene dichloride or methylene dichloride and chlorobenzene.
The phase interface polycondensation can be passed through for example tertiary amine of catalyzer, and especially N-Alkylpiperidine class or  salt quicken.Tributylamine, triethylamine and N-ethylpiperidine are preferred the uses.In the melt transesterification method, the preferred catalyzer of in DE-A 4 238 123, enumerating that uses.
Polycarbonate can pass through to use a spot of branching agent branching with controllable manner wittingly.Some branching agents that are fit to are: Phloroglucinol, 4,6-dimethyl-2,4,6-three-(4-hydroxyphenyl) heptene-2; 4,6-dimethyl-2,4,6-three-(4-hydroxyphenyl) heptane; 1,3,5-three-(4-hydroxyphenyl) benzene; 1,1,1-three-(4-hydroxyphenyl) ethane; Three-(4-hydroxyphenyl) phenylmethanes; 2,2-pair-[4,4-pair-(4-hydroxyphenyl) cyclohexyl] propane; 2,4-pair-(4-hydroxyphenyl sec.-propyl) phenol; 2,6-pair-(2-hydroxyl-5 '-methyl-benzyl)-4-methylphenol; 2-(4-hydroxyphenyl)-2-(2, the 4-dihydroxy phenyl) propane; Six-(4-(4-hydroxyphenyl sec.-propyl) phenyl) adjacency pair phthalic acid esters; Four-(4-hydroxyphenyl) methane; Four-(4-(4-hydroxyphenyl sec.-propyl) phenoxy group) methane; α, α, α '-three-(4-hydroxyphenyl)-1,3,5-triisopropylbenzene; 2, the 4-resorcylic acid; Trimesic acid; Cyanuric chloride; 3,3-pair-(3-methyl-4-hydroxyphenyl)-2-oxo-2, the 3-indoline; 1,4-is two-(4 ', 4 "-dihydroxyl triphenyl) methyl) benzene and especially: 1,1,1-three-(4-hydroxyphenyl) ethane and pair-(3-methyl-4-hydroxyphenyl)-2-oxo-2, the 3-indoline.
In employed diphenol is benchmark, and the optional shared branching agent of 0.05-2mol% or the mixture of branching agent can add with diphenol, but also can add in synthesis phase afterwards.
Phenol such as phenol, alkylphenol such as cresols and 4-tert.-butyl phenol, chlorophenol, bromine phenol, cumyl phenol or their mixture are preferably used as chain terminator, and its amount is 1-20mol%, the bis-phenol of preferred 2-10mol%/mol.Phenol, 4-tert.-butyl phenol or cumyl phenol are preferred.
Chain terminator and branching agent can be separately or with bis-phenol join synthetic in.
For example, the method for preparing polycarbonate by the melt transesterification method has been described in DE-A 42 38 123.
Preferred polycarbonate is based on the homo-polycarbonate of dihydroxyphenyl propane, based on 1,1-pair-(4-hydroxyphenyl)-3,3, the homo-polycarbonate of 5-trimethyl-cyclohexane is based on two kinds of monomer dihydroxyphenyl propanes and 1,1-pair-(4-hydroxyphenyl)-3,3, the Copolycarbonate of 5-trimethyl-cyclohexane and based on two kinds of monomer dihydroxyphenyl propanes and 4, the Copolycarbonate of 4 '-dihydroxybiphenyl (DOD).
Homo-polycarbonate based on dihydroxyphenyl propane is especially preferred.
All thermoplastic materials that use in product according to the present invention can contain stablizer.The stablizer that is fit to for example is to contain the stablizer of phosphine class, phosphorous acid ester or Si and at other compound described in the EP-A 0,500 496.Triphenyl phosphite, phosphorous acid diphenyl alkyl ester, phosphorous acid phenyl dialkyl ester, tricresyl phosphite (nonyl phenyl) ester, four-(2, the 4-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates and triaryl phosphites can be used as example and enumerate.Triphenylphosphine and three-(2, the 4-di-tert-butyl-phenyl) phosphorous acid ester is particularly preferred.
These stablizers may reside in according to multilayer product of the present invention all the layer in.In other words, in so-called substrate and in so-called coextrusion layer, can there be the different additives or the additive of different concns in each layer.
The monohydroxy-alcohol that can also comprise 0.01-0.5wt% according to multilayer product of the present invention is to hexavalent alcohol, especially the ester or the partial ester of glycerine, tetramethylolmethane or Guerbet (Guerbet) alcohol.
Monohydroxy-alcohol for example is stearyl alcohol, palmityl alcohol and Guerbet alcohol.
The example of dibasic alcohol is an ethylene glycol.
The example of trivalent alcohol is a glycerine.
The example of tetravalent alcohol is tetramethylolmethane and mesoerythrit.
The example of pentavalent alcohol is an arabitol, ribitol and Xylitol.
The example of hexavalent alcohol is a N.F,USP MANNITOL, glucitol (sorbyl alcohol) and melampyrum.
The aliphatic C that described ester is preferably saturated 10-C 36Monocarboxylic acid and optional hydroxyl monocarboxylic acid, preferred saturated aliphatic C 14-C 32Monoesters, diester, three esters, four esters, five-ester and six esters or their mixture, the especially random mixture of monocarboxylic acid and the hydroxyl monocarboxylic acid of choosing wantonly.
Because production method, commercially available fatty acid ester, especially the fatty acid ester of tetramethylolmethane and glycerine can contain＜60% various partial esters.
Saturated aliphatic mono with 10-36 C atom for example is capric acid, dodecylic acid, tetradecanoic acid, hexadecanoic acid, stearic acid, oxystearic acid, arachic acid, docosoic acid, Lignoceric acid, hexacosanoic acid and octocosoic acid.
Saturated, the mono carboxylic acid of aliphatic series that preferably have 14-22 C atom for example are tetradecanoic acid, hexadecanoic acid, stearic acid, oxystearic acid, arachic acid and docosoic acid.
Saturated mono carboxylic acid of aliphatic series, hexadecanoic acid for example, stearic acid and oxystearic acid are particularly preferred.
Radical of saturated aliphatic C 10-C 36Itself can learn carboxylic acid and fatty acid ester from document, perhaps can prepare by the method for learning from document.The example of pentaerythritol fatty ester is those of above-mentioned particularly preferred monocarboxylic acid.
The ester of tetramethylolmethane and glycerine and stearic acid and hexadecanoic acid is particularly preferred.
The ester of pure and mild glycerine of Guerbet and stearic acid and hexadecanoic acid and optional and oxystearic acid also is particularly preferred.
These esters can be present in substrate and the coextrusion layer.The additive that in each layer, can have different additive or different concns.
Can contain static inhibitor according to multilayer product of the present invention.
The example of static inhibitor is a cation compound, quaternary ammonium for example,  salt or sulfonium salt, anionic compound, alkylsulfonate for example, alkyl-sulphate, alkylphosphonic, the carboxylate salt of an alkali metal salt or alkaline-earth metal salt form, the nonionic endogenous compound, macrogol ester for example, polyglycol ether, fatty acid ester, ethoxylated fatty amine.
These static inhibitor may reside in substrate and the coextrusion layer.In each layer, can there be different additives or concentration.They are preferred for the coextrusion layer.
Can contain organic dye according to multilayer product of the present invention, inorganic coloring pigment, fluorescence dye and especially preferred white dyes.
These tinting materials can be present in substrate and the coextrusion layer.In each layer, can there be different additives or concentration.
Owing to produce and condition of storage, all moulding compounds, its raw material and the solvent that are used to prepare according to multilayer product of the present invention may be by corresponding contaminating impurities, and target is to operate with the purest as far as possible starting raw material here.
Each component in the moulding compound can be mixed in room temperature with under heating up continuously and simultaneously by known way.
Additive, especially above-mentioned additive, preferably press known way by with polymer beads and additive under about 200-330 ℃ the temperature at common unit for example in internal mixer, single screw extrusion machine and the biaxial extruder, for example by melt compounded or melt extrusion or by polymers soln is mixed with the solution of additive, be incorporated into the moulding compound that is used for according to product of the present invention by evaporating solvent in a known manner subsequently.Additive level in the moulding compound can change in the tolerance, and controls by the desired properties of moulding compound.Additive level in the moulding compound is about 20wt% at the most preferably, and more preferably 0.2-12wt% is a benchmark in the weight of moulding compound.
Coextrusion itself can be learnt (for example referring to EP-A 0 110 221 and EP-A0 110 238) from document.In this case, schedule of operation is preferably as follows and carries out.Forcing machine is connected in the coextrusion joint, to produce core and skin.This joint designs as the mode that thin layer adheres to the melt of core so that form outer field melt.The multilayer melt wire rod of Sheng Chaning is transferred in the adjacent die head with desired form (multi-layer sheet or solid sheet) then like this.This melt cools off by calendering (solid sheet) or Vacuum shaping (multi-layer sheet) by known way then under controlled conditions, cuts into certain-length then.After the typing stage, can choose wantonly to connect and regulate baking oven to eliminate stress.The joint that replacement connects before die head, the mode that die head itself can also make melt flock together designs.
Can also prepare multilayer materials by extrusion coated, coextrusion and coextrusion blowing according to prior art.
Further specify the present invention by the following examples, but the invention is not restricted to these embodiment.According to embodiments of the invention the preferred embodiments of the invention have only been described.
Embodiment
Embodiment 1
Synthesize equal polyformal by bis-phenol TMC:
Under nitrogen protection gas; when stirring; with the bis-phenol TMC of 7kg (22.55mol), the finely powdered p-tert-butylphenol (Aldrich) of the sodium hydroxide pellets of 2.255kg (56.38mol) and the 51.07g (0.34mol) in the 500ml methylene dichloride joins in the solvent blend of being made up of the N-N-methyl-2-2-pyrrolidone N-(NMP) of the methylene dichloride of 28.7kg and 40.18kg.After homogenizing, this mixture is refluxed (78 ℃), under this temperature, stirred 1 hour.After being cooled to 25 ℃, this reaction batch of material dilutes with the methylene dichloride of 35L and the softening water of 20L.This batch of material water washs in separator, is neutral and saliferous (electric conductivity＜15 μ S.cm not up to it -1).From separator, isolate organic phase, in vaporizer, carry out the exchange of solvent of methylene dichloride and chlorobenzene.This material is extruded granulation then with ZSK 32 evaporation forcing machines then under 270 ℃ temperature.This synthesis procedure carries out twice.After abandoning raw material, obtained to be the polyformal of the 9.85kg altogether of transparent grain.This still contains the lower molecular weight cyclic formals as impurity.This material is divided into two portions, and each part is with the acetone swelling a whole night of about 5L.Products therefrom is with several parts of fresh acetone compoundings, up to no longer detecting ring compound.After the material of will purify merged and is dissolved in it in the chlorobenzene, it was extruded under 280 ℃ by the evaporation forcing machine once more.After abandoning raw material, obtained to be the polyformal of the 7.31kg altogether of transparent grain.
Analyze:
Molecular weight Mw=38345, Mn=20138, D=1.90 (GPC calibrates with polycarbonate)
Glass transition temperature Tg=170.8 ℃
Relative solution viscosity in the methylene dichloride (0.5g/100ml solution)=1.234
Confirm that by GPC (oligopolymer of lower molecular weight scope) and MALDI-TOF (with the molecular weight of the molecular weight ratio ring compound of open chain analogue) polymkeric substance does not contain ring compound.
Embodiment 2
Synthesize equal polyformal by dihydroxyphenyl propane:
Figure A20058000258500191
Under nitrogen protection gas; when stirring; with the dihydroxyphenyl propane (Bayer AG) of 7kg (30.66mol), the finely powdered p-tert-butylphenol (Aldrich) of the sodium hydroxide pellets of 3.066kg (76.65mol) and the 69.4g (0.462mol) in the 500ml methylene dichloride joins in the solvent blend of being made up of the N-N-methyl-2-2-pyrrolidone N-(NMP) of the methylene dichloride of 28.7kg and 40.18kg.After homogenizing, this mixture is refluxed (78 ℃), under this temperature, stirred 1 hour.After being cooled to 25 ℃, this reaction batch of material dilutes with the methylene dichloride of 20L and the softening water of 20L.This batch of material water washs in separator, is neutral and saliferous (electric conductivity＜15 μ S.cm not up to it -1).From separator, isolate organic phase, in vaporizer, carry out the exchange of solvent of methylene dichloride and chlorobenzene.This material is extruded granulation then with ZSK 32 evaporation forcing machines then under 200 ℃ temperature.This synthesis procedure carries out twice.After abandoning raw material, obtained to be the polyformal of the 11.99kg altogether of transparent grain.
Analyze:
Molecular weight Mw=31732, Mn=3465 (GPC calibrates with polycarbonate).In this case, do not isolate ring compound.This material is impossible with the acetone swelling, and the separation that this means ring compound is impossible equally
Glass transition temperature Tg=89 ℃
Relative solution viscosity in the methylene dichloride (0.5g/100ml solution)=1.237/1.239 (secondary mensuration).
Embodiment 3
A) by bis-phenol TMC and the synthetic copolymerization formal of dihydroxyphenyl propane:
Figure A20058000258500201
Under nitrogen protection gas; when stirring; bis-phenol TMC (x=70mol%) with 5.432kg (17.5mol); 1.712kg dihydroxyphenyl propane (7.5mol) (y=30mol%), the finely powdered p-tert-butylphenol (Aldrich) of the sodium hydroxide pellets of 2.5kg (62.5mol) and the 56.33g (0.375mol) in the 500ml methylene dichloride joins in the solvent blend of being made up of the N-N-methyl-2-2-pyrrolidone N-(NMP) of the methylene dichloride of 28.7kg and 40.18kg.After homogenizing, this mixture is refluxed (78 ℃), under this temperature, stirred 1 hour.After being cooled to 25 ℃, this reaction batch of material dilutes with the methylene dichloride of 35L and the softening water of 20L.This batch of material water washs in separator, is neutral and saliferous (electric conductivity＜15 μ S.cm not up to it -1).From separator, isolate organic phase, in vaporizer, carry out the exchange of solvent of methylene dichloride and chlorobenzene.This material is extruded granulation then with ZSK 32 evaporation forcing machines then under 280 ℃ temperature.After abandoning raw material, obtained to be the copolymerization formal of the 5.14kg altogether of transparent grain.This still contains the lower molecular weight ring compound as impurity.With the acetone swelling a whole night of this material with about 5L.Products therefrom is with several parts of fresh acetone compoundings, up to no longer detecting ring compound., in chlorobenzene, extrude under 270 ℃ by the evaporation forcing machine once more in the material dissolves of will purify.After abandoning raw material, obtained to be the polyformal of the 3.11kg altogether of transparent grain.
Analyze:
Molecular weight Mw=39901, Mn=19538, D=2.04 (GPC calibrates with polycarbonate)
Glass transition temperature Tg=148.2 ℃
Relative solution viscosity in the methylene dichloride (0.5g/100ml solution)=1.244/1.244 (particle)
CDCl 3In 1H-NMR shows that the monomeric expection insertion of TMC/BPA is than x/y=0.7/0.3 (integration of the chemical shift of cycloaliphatic groups (TMC) and methyl (BPA)).
B)-i) under the situation that changes composition, synthesize the copolymerization formal by bis-phenol TMC and dihydroxyphenyl propane:
According to embodiment 3a) identical mode prepares other copolymerization formal (referring to table 1):
Embodiment number TMC[mol％] BPA[mol％] Tg[℃]
3b) 3c) 3d) 3e) 3f) 30 35 40 50 55 70 65 60 50 45 115 120 124 132 137
3g) 3h) 3i) 70 80 90 30 20 10 149 158 165
Embodiment 4
By bis-phenol TMC and 4,4 '-dihydroxybiphenyl (DOD) synthesizes the copolymerization formal:
Under nitrogen protection gas; when stirring; bis-phenol TMC (x=90mol%) with 3.749kg (12.07mol); 0.2497kg (1.34mol) 4; 4 '-dihydroxybiphenyl (DOD) (y=10mol%), the finely powdered p-tert-butylphenol (Aldrich) of the sodium hydroxide pellets of 1.339kg (33.48mol) and the 20.12g (0.134mol) in the 200ml methylene dichloride joins in the solvent blend of being made up of the N-N-methyl-2-2-pyrrolidone N-(NMP) of the methylene dichloride of 12.0L and 22.25kg.After homogenizing, this mixture is refluxed (78 ℃), under this temperature, stirred 1 hour.After being cooled to 25 ℃, this reaction batch of material dilutes with the methylene dichloride of 35L and the softening water of 20L.This batch of material water washs in separator, is neutral and (electric conductivity＜15 μ S.cm till the saliferous not up to it -1).From separator, isolate organic phase, in vaporizer, carry out the exchange of solvent of methylene dichloride and chlorobenzene.This material is extruded granulation then with ZSK 32 evaporation forcing machines then under 280 ℃ temperature.After abandoning raw material, obtained to be the copolymerization formal of the 2.62kg altogether of transparent grain.This still contains the lower molecular weight ring compound as impurity.With the acetone swelling a whole night of this material with about 5L.Products therefrom is with several parts of fresh acetone compoundings, up to no longer detecting ring compound., in chlorobenzene, extrude under 240 ℃ by the evaporation forcing machine once more in the material dissolves of will purify.After abandoning raw material, obtained to be the polyformal of transparent grain.
Analyze:
Molecular weight Mw=44287, Mn=17877, D=2.48 (GPC calibrates with polycarbonate)
Glass transition temperature Tg=167 ℃.
Embodiment 5
By dihydroxyphenyl propane and 4,4 '-dihydroxybiphenyl (DOD) synthesizes the copolymerization formal:
Figure A20058000258500231
Under nitrogen protection gas; when stirring; dihydroxyphenyl propane (x=70mol%) with 22.37g (0.0098mol); 7.82g (0.0042mol) 4; 4 '-dihydroxybiphenyl (DOD) (y=30mol%), the finely powdered p-tert-butylphenol (Aldrich) of the sodium hydroxide pellets of 14.0g (0.35mol) and 0.21g (0.0014mol) joins in the solvent blend of being made up of the N-N-methyl-2-2-pyrrolidone N-(NMP) of the methylene dichloride of 125ml and 225ml.After homogenizing, this mixture is refluxed (78 ℃), under this temperature, stirred 1 hour.After being cooled to 25 ℃, this reaction batch of material dilutes with methylene dichloride and softening water.Washing with water then, is neutral and (electric conductivity＜15 μ S.cm till the saliferous not up to it -1).Isolate organic phase.This polymkeric substance separates by precipitating in methyl alcohol.In water and methanol wash and after 80 ℃ of following dryings, the polyformal of the polymer filaments that obtained to be white in color.
Analyze:
Molecular weight Mw=19057, Mn=4839, D=3.94 (GPC calibrates with polycarbonate).
Embodiment 6
The hydrolysis experiment of the BPA polyformal of embodiment 2:
By adopting following hydrolysis medium/temperature condition and changing the test that is hydrolyzed by the time dependent molecular weight of measuring in the methylene dichloride of relative solution viscosity (0.5g/100ml solution) mensuration:
Hydrolysis medium: 0.1N HCl/80 ℃
0.1N NaOH/80℃
Distilled water/about 100 ℃
Obtained following result (under each situation, repeatedly measuring) in cycle in the total load that reaches 21 days:
A) hydrolysis medium: 0.1N HCl/80 ℃
Time [fate] relative solution viscosity η Rel
0 1.237/1.239 (reference sample)
7 1.237/1.238/1.236/1.237/1.237/1.238
14 1.237/1.237/1.236/1.237/1.237/1.237
21 1.236/1.239/1.235/1.236/1.235/1.235
A) hydrolysis medium: 0.1N NaOH/80 ℃
Time [fate] relative solution viscosity η Rel
0 1.237/1.239 (reference sample)
7 1.237/1.238/1.237/1.237/1.236/1.237
14 1.237/1.237/1.236/1.236/1.236/1.236
21 1.236/1.236/1.236/1.236/1.236/1.235
A) hydrolysis medium: distilled water/about 100 ℃
Time [fate] relative solution viscosity η Rel
0 1.237/1.239 (reference sample)
7 1.238/1.237/1.238/1.237/1.237/1.237
14 undetermineds
21 1.238/1.237/1.237/1.237/1.237/1.235
Embodiment 7
The hydrolysis experiment of the TMC/BPA copolymerization formal (70/30) of embodiment 3:
By adopting following hydrolysis medium/temperature condition and changing the test that is hydrolyzed by the time dependent molecular weight of measuring in the methylene dichloride of relative solution viscosity (0.5g/100ml solution) mensuration:
Hydrolysis medium: 0.1N HCl/80 ℃
0.1N NaOH/80℃
Distilled water/about 100 ℃
Obtained following result (under each situation, repeatedly measuring) in cycle in the total load that reaches 21 days:
A) hydrolysis medium: 0.1N HCl/80 ℃
Time [fate] relative solution viscosity η Rel
0 1.242/1.242 (reference sample; Be sprayed to
After on 80 * 10 * 4 test specimens)
7 1.242/1.242/1.243/1.243/1242/1.243
14 1.240/1.241/1.240/1.242/1.241/1.241
21 1.243/1.243/1.243/1.242/1.243/1.243
A) hydrolysis medium: 0.1N NaOH/80 ℃
Time [fate] relative solution viscosity η Rel
0 1.242/1.242 (reference sample)
7 1.243/1.242/1.243/1.243/1.243/1.243
14 1.240/1.241/1.241/1.241/1.242/1.242
21 1.242/1.242/1.243/1.242/1.243/1.242
A) hydrolysis medium: distilled water/about 100 ℃
Time [fate] relative solution viscosity η Rel
0 1.242/1.242 (reference sample)
7 1.242/1.243/1.242/1.243/1.243/1.242
14 1.241/1.241/1.241/1.242/1.241/1.241
21 1.242/1.243/1.242/1.241/1.244/1.243
Embodiment 8
The hydrolysis experiment of TMC polyformal:
(identical with embodiment 1, but have more high molecular)
Molecular weight Mw=50311, Mn=21637, D=2.32 (GPC calibrates with polycarbonate)
Glass transition temperature Tg=172 ℃
Relative solution viscosity in the methylene dichloride (0.5g/100ml solution)=1.288/1.290
By adopting following hydrolysis medium/temperature condition and changing the test that is hydrolyzed by the time dependent molecular weight of measuring in the methylene dichloride of relative solution viscosity (0.5g/100ml solution) mensuration:
Hydrolysis medium: 0.1N HCl/80 ℃
0.1N NaOH/80℃
Distilled water/about 100 ℃
Obtained following result (under each situation, repeatedly measuring) in cycle in the total load that reaches 21 days:
A) hydrolysis medium: 0.1N HCl/80 ℃
Time [fate] relative solution viscosity η Rel
0 1.288/1.290 (reference sample; Be sprayed to
After on 80 * 10 * 4 test specimens)
7 1.291/1.290/1.289/1.288/1.288/1.290
14 1.288/1.288/1.289/1.289/1.288/1.288
21 1.288/1.288/1.289/1.289/1.289/1.289
A) hydrolysis medium: 0.1N NaOH/80 ℃
Time [fate] relative solution viscosity η Rel
0 1.288/1.290 (reference sample)
7 1.289/1.289/1.290/1.290/1.289/1.289
14 1.287/1.289/1.288/1.289/1.286/1.287
21 1.287/1.288/1.294/1.294/1.288/1.288
A) hydrolysis medium: distilled water/about 100 ℃
Time [fate] relative solution viscosity η Rel
0 1.288/1.290 (reference sample)
7 1.285
14 1.281
21 1.284
Embodiment 9
The hydrolysis experiment (contrast experiment) of the polycarbonate Makrolon  2808 of Bayer AG:
By adopting following hydrolysis medium/temperature condition and changing the test that is hydrolyzed by the time dependent molecular weight of measuring in the methylene dichloride of relative solution viscosity (0.5g/100ml solution) mensuration:
Hydrolysis medium: 0.1N HCl/80 ℃
0.1N NaOH/80℃
Distilled water/about 100 ℃
Obtained following result (under each situation, repeatedly measuring) in cycle in the total load that reaches 21 days:
A) hydrolysis medium: 0.1N HCl/80 ℃
Time [fate] relative solution viscosity η Rel
0 1.284/1.289 (reference sample; Be sprayed to
After on 80 * 10 * 4 test specimens)
7 1.282/1.280/1.281/1.283/1.278/1.280
14 1.280/1.281/1.278/1.279/1.280/1.280
21 1.275/1.276/1.276/1.276/1.277/1.277
A) hydrolysis medium: 0.1N NaOH/80 ℃
Time [fate] relative solution viscosity η Rel
0 1.284/1.289 (reference sample)
7 1.279/1.280/1.279/1.279/1.280/1.280
14 1.277/1.277/1.277/1.277/1.279/1.279
21 1.277/1.277/1.274/1.274/1.279/1.282
A) hydrolysis medium: distilled water/about 100 ℃
Time [fate] relative solution viscosity η Rel
0 1.284/1.289 (reference sample)
7 1.272
14 1.273
21 1.273
Obviously as can be seen, compare with polyformal, the soltion viscosity of polycarbonate descends more sharp after hydrolysis loads.This means that polycarbonate can easier degraded, therefore more unstable.Coextrusion layer by the polyformal preparation therefore can be as preventing sheet material or the too early destructive protective layer of container.
Embodiment 10
Synthesize the copolymerization formal by bis-phenol TMC and Resorcinol:
Under nitrogen protection gas; when stirring; bis-phenol TMC (x=90mol%) with 39.1g (0.126mol); 1.542g Resorcinol (0.014mol) (y=10mol%), the finely powdered p-tert-butylphenol (Aldrich) of the sodium hydroxide pellets of 14.0g (0.35mol) and 0.21g (0.0014mol) joins in the solvent blend of being made up of the N-N-methyl-2-2-pyrrolidone N-(NMP) of the methylene dichloride of 125ml and 225ml.After homogenizing, this mixture is refluxed (78 ℃), under this temperature, stirred 1 hour.After being cooled to 25 ℃, this reaction batch of material dilutes with methylene dichloride and softening water.Washing with water then, is neutral and (electric conductivity＜15 μ S.cm till the saliferous not up to it -1).Isolate organic phase.This polymkeric substance separates by precipitating in methyl alcohol.In water and methanol wash, go out ring compound and after 80 ℃ of following dryings with acetone separation, the polyformal of the polymer filaments that obtained to be white in color.
Analyze:
Molecular weight Mw=32008, Mn=12251, D=2.6 (GPC calibrates with polycarbonate)
Glass transition temperature Tg=163 ℃.
Embodiment 11
By bis-phenol TMC and, right-dihydroxyphenyl propane synthesizes the copolymerization formal:
Under nitrogen protection gas; when stirring; bis-phenol TMC (x=50mol%) with 14.84g (0.065mol); 20.18g (0.065mol); right-dihydroxyphenyl propane (3; 4-isopropylidene diphenol) (y=50mol%), the finely powdered p-tert-butylphenol (Aldrich) of the sodium hydroxide pellets of 14.0g (0.35mol) and 0.21g (0.0014mol) joins in the solvent blend of being made up of the N-N-methyl-2-2-pyrrolidone N-(NMP) of the methylene dichloride of 125ml and 225ml.After homogenizing, this mixture is refluxed (78 ℃), under this temperature, stirred 1 hour.After being cooled to 25 ℃, this reaction batch of material washes with water then with the dilution of methylene dichloride and softening water, is neutral and (electric conductivity＜15 μ S.cm till the saliferous not up to it -1).Isolate organic phase.This polymkeric substance separates by precipitating in methyl alcohol.In water and methanol wash, go out ring compound and after 80 ℃ of following dryings with acetone separation, the polyformal of the polymer filaments that obtained to be white in color.
Analyze:
Molecular weight Mw=28254, Mn=16312, D=1.73 (GPC calibrates with polycarbonate)
Glass transition temperature Tg=92 ℃.
Embodiment 12
By dihydroxyphenyl propane and 4,4 '-sulfone diphenol synthesizes the copolymerization formal:
Figure A20058000258500311
Under nitrogen protection gas; when stirring; with 4 of 36.29g (0.145mol); 4 '-sulfone diphenol (x=50mol%); 33.46g dihydroxyphenyl propane (0.145mol) (y=50mol%), the finely powdered p-tert-butylphenol (Aldrich) of the sodium hydroxide pellets of 28.8g (0.72mol) and 0.436g (0.0029mol) joins in the solvent blend of being made up of the N-N-methyl-2-2-pyrrolidone N-(NMP) of the methylene dichloride of 300ml and 570ml.After homogenizing, this mixture is refluxed (78 ℃), under this temperature, stirred 1 hour.After being cooled to 25 ℃, this reaction batch of material washes with water then with the dilution of methylene dichloride and softening water, is neutral and (electric conductivity＜15 μ S.cm till the saliferous not up to it -1).Isolate organic phase.This polymkeric substance separates by precipitating in methyl alcohol.In water and methanol wash, go out ring compound and after 80 ℃ of following dryings with acetone separation, the polyformal of the polymer filaments that obtained to be white in color.
Analyze:
Molecular weight Mw=21546, Mn=7786, D=2.76 (GPC calibrates with polycarbonate)
Glass transition temperature Tg=131 ℃.
Embodiment 13
By 4,4 '-dihydroxy phenyl ether synthesizes polyformal:
Under nitrogen protection gas; when stirring; with 4 of 28.30g (0.14mol); 4 '-dihydroxy phenyl ether (Bayer AG), the finely powdered p-tert-butylphenol (Aldrich) of the sodium hydroxide pellets of 14.0g (0.35mol) and 0.21g (0.0014mol) joins in the solvent blend of being made up of the N-N-methyl-2-2-pyrrolidone N-(NMP) of the methylene dichloride of 125ml and 225ml.After homogenizing, this mixture is refluxed (78 ℃), under this temperature, stirred 1 hour.After being cooled to 25 ℃, this reaction batch of material washes with water then with the dilution of methylene dichloride and softening water, is neutral and (electric conductivity＜15 μ S.cm till the saliferous not up to it -1).Isolate organic phase.This polymkeric substance separates by precipitating in methyl alcohol.In water and methanol wash, go out ring compound and after 80 ℃ of following dryings with acetone separation, the polyformal of the polymer filaments that obtained to be white in color.
Analyze:
Molecular weight Mw=24034, Mn=9769, D=2.46 (GPC calibrates with polycarbonate)
Glass transition temperature Tg=57 ℃.

Claims (4)

1. at least a polyformal or copolymerization formal are used to produce the purposes of the hydrolysising protection coating that is used for container.
2. purposes according to claim 1 is characterised in that this polyformal or copolymerization formal have following general formula (1a) or (1b):
Figure A2005800025850002C1
Wherein group O-D-O and O-E-O represent any diphenol foundation group, wherein-D-and-E-is the aromatic group with 6-40 C atom, described group can contain one or more aromatics or fused aromatic nuclear, and this nuclear is optional to contain heteroatoms, and described group is optional by C 1-C 12Alkyl or halogen replace and can contain aliphatic group, cycloaliphatic groups, aromatic kernel or heteroatoms are as connecting base, and wherein k represents the integer of 1-1500, and m represents that mark z/o and n represent mark (o-z)/o, wherein z represents the numerical value of 0-o, and group-O-D-O-and-part of O-E-O-also represents like this, to have occurred the 3rd bound fraction in this by one or more trifunctional compound deutero-groups independently of one another, that is the branch of polymer chain.
3. has container according to the hydrolysising protection coating of claim 1 or 2.
4. have water bottle, infant bottle and medical product according to the hydrolysising protection coating of claim 1 or 2.
CNA200580002585XA 2004-01-16 2005-01-07 Polyformals and copolyformals as hydrolysis protection layers on polycarbonates Pending CN1910213A (en)

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