Patent Application
20110257335
The invention relates to a block copolymer with weight-average molar mass Mw of at least 100 000 g/mol, comprising
a) at least one block S composed of from 95 to 100% by weight of vinylaromatic monomers and from 0 to 5% by weight of dienes, and
b) at least one copolymer block (S/B)A composed of from 63 to 80% by weight of vinylaromatic monomers and from 20 to 37% by weight of dienes, with glass transition temperature TgA in the range from 5 to 30° C., and
c) at least one copolymer block (S/B)B composed of from 20 to 60% by weight of vinylaromatic monomers and from 40 to 80% by weight of dienes, with glass transition temperature TgB in the range from 0 to −80° C.,
where the proportion by weight of the entirety of all of the blocks S is in the range from 50 to 70% by weight, and the proportion by weight of the entirety of all of the blocks (S/B)A and (S/B)B is in the range from 30 to 50% by weight, based in each case on the block copolymer A, and also mixtures thereof, and their use.
U.S. Pat. No. 3,639,517 describes star-shaped branched styrene-butadiene block copolymers having from 75 to 95 percent by weight of terminal blocks composed of vinylaromatic monomers, and from 5 to 30 percent by weight of elastomeric blocks mainly composed of conjugated diene units. They can be blended with standard polystyrene to give highly transparent mixtures. With increasing proportion of polystyrene, modulus of elasticity rises, with attendant losses in toughness. Mixtures using as little as 40 percent by weight of polystyrene are too brittle for most applications. If acceptable ductility is to be retained, the possible admixture of polystyrene is mostly only 20, up to a maximum of 30, percent by weight.
Star-shaped block copolymers having 40% by weight of hard blocks composed of vinylaromatic monomers, and soft blocks having random structure composed of vinylaromatic monomers and dienes, are described in WO 00/58380. They are blended with standard polystyrene in order to increase stiffness, whereupon transparency falls. Even with 60 percent by weight of polystyrene, they continue to give ductile mixtures. The disadvantage of these blends is the clearly visible haze, which is unacceptable for more demanding applications and thicker components.
WO 2006/074819 describes mixtures of from 5 to 50% by weight of a block copolymer A, which comprises one or more copolymer blocks (B/S)A in each case composed of from 65 to 95% by weight of vinylaromatic monomers and from 35 to 5% by weight of dienes, with glass transition temperature TgA in the range from 40° to 90° C., and from 95 to 50% by weight of a block copolymer B which comprises at least one hard block S composed of vinylaromatic monomers, and one or more copolymer blocks (B/S)B in each case composed of from 20 to 60% by weight of vinylaromatic monomers and from 80 to 40% by weight of dienes, with glass transition temperature TgB in the range from −70° to 0° C., for the production of shrink foils. The stiffness of the mixtures is in the range from 700 to a maximum of 1300 MPa.
EP-A 1 669 407 discloses mixtures composed of linear block copolymers composed of vinylaromatic monomers and dienes of the structure (I) S1-B1-S2 and (II) B2-S3. The blocks B1 and B2 can be composed exclusively of dienes, or of dienes and vinylaromatic monomers. The ratio by weight of vinylaromatic monomer to diene for the blocks B1 and B2 is preferably in the range from 0.3 to 1.5.
PCT/EP2008/061635, as yet unpublished, describes transparent, tough and stiff molding compositions based on styrene-butadiene block copolymer mixtures which can comprise, inter alia, from 0 to 30% by weight of a block copolymer which comprises at least one copolymer block (B/S)A in each case composed of from 65 to 95% by weight of vinylaromatic monomers and from 35 to 5% by weight of dienes, with glass transition temperature TgA in the range from 40 to 90° C., and at least one copolymer block (B/S)B in each case composed of from 1 to 60% by weight of vinylaromatic monomers and from 99 to 40% by weight of dienes, with glass transition temperature TgB in the range from −100 to 0° C.
Any desired modulus of elasticity extending to above 3000 MPa can be obtained via blending of conventional styrene-butadiene block copolymers, such as Styrolux®, with polystyrene, as a function of mixing ratio. However, experience has shown that no useful ductility is retained when the modulus of elasticity is above 1900 MPa. The mechanical behavior of the mixtures is then similar to that of polystyrene itself, and they then have no advantages over the latter.
Blister packs, thermoformed containers and pots, and packaging materials for electronic components, for example extruded hollow profiles used as transport tubes for integrated circuits, require a combination of high stiffness and ductility and good transparency, while dependably exceeding the required yield stress value. These are applications for which polystyrene and its mixtures with styrene-butadiene block copolymers have hitherto had no, or only limited, suitability. The market has hitherto been covered by polyvinyl chloride (PVC), and to some extent by polyethylene terephthalates (PET), or very expensive specialty polymers.
It was an object of the invention to find block copolymers which can be processed with polystyrenes to give transparent molding compositions which are tough and stiff. The mixtures should be processible to give molding compositions with high stiffness, and in particular have a modulus of elasticity of from more than 1900 to 2500 MPa, combined with a particular ductility in the tensile test.
Accordingly, the abovementioned block copolymers have been found, as also have mixtures with further styrene polymers.
Surprisingly, it has now been found that the block copolymer of the invention, which comprises one or more blocks S/B with glass transition temperature in the range from 5 to 30° C., forms the soft phase in molding compositions composed of polystyrene or of polymers comprising polystyrene blocks, and, in comparison with conventional molding compositions composed of block copolymers having butadiene-rich blocks, have markedly increased yield stress, and higher modulus of elasticity, together with good ductility.
The block copolymer of the invention has a weight-average molar mass KA, of at least 100 000 g/mol and comprises
a) at least one block S composed of from 95 to 100% by weight of vinylaromatic monomers and from 0 to 5% by weight of dienes, and
b) at least one copolymer block (S/B)A composed of from 63 to 80% by weight of vinylaromatic monomers and from 20 to 37% by weight of dienes, with glass transition temperature TgA in the range from 5 to 30° C., and
c) at least one copolymer block (S/B)B composed of from 20 to 60% by weight of vinylaromatic monomers and from 40 to 80% by weight of dienes, with glass transition temperature TgB in the range from 0 to −80° C.,
where the proportion by weight of the entirety of all of the blocks S is in the range from 50 to 70% by weight, and the proportion by weight of the entirety of all of the blocks (S/B)A and (S/B)B is in the range from 30 to 50% by weight, based in each case on the block copolymer A.
Examples of vinylaromatic monomers that can be used are styrene, alpha-methylstyrene, ring-alkylated styrenes, such as p-methylstyrene, or tert-butylstyrene, or 1,1-diphenylethylene, or a mixture thereof. It is preferable to use styrene.
Preferred dienes are butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, or piperylene, or a mixture of these. Particular preference is given to butadiene and isoprene.
The weight-average molar mass Mw of the block copolymer is preferably in the range from 250 000 to 350 000 g/mol.
The blocks S are preferably composed of styrene units. In the case of the polymers produced via anionic polymerization, the molar mass is controlled by way of the ratio of amount of monomer to amount of initiator. However, initiator can also be added a number of times after completion of monomer feed, the product then being bi- or multimodal distribution. In the case of polymers produced by a free-radical route, the weight-average molecular weight Mw is set by way of the polymerization temperature and/or addition of regulators.
The glass transition temperature of the copolymer block (S/B)A is preferably in the range from 5 to 20° C. The glass transition temperature is affected by the comonomer constitution and comonomer distribution, and can be determined via Differential Scanning Calorimetry (DSC) or Differential Thermal Analysis (DTA), or can be calculated from the Fox equation. The glass transition temperature is generally determined using DSC to ISO 11357-2 with a heating rate of 20 K/min.
The copolymer block (S/B)A is preferably composed of from 65 to 75% by weight of styrene and from 25 to 35% by weight of butadiene.
Preference is given to block copolymers which comprise one or more copolymer blocks (S/B)A composed of vinylaromatic monomers and dienes with random distribution.
These can by way of example be obtained via anionic polymerization using alkyllithium compounds in the presence of randomizers, such as tetrahydrofuran, or potassium salts. Preference is given to use of potassium salts, using a ratio of anionic initiator to potassium salt in the range from 25:1 to 60:1. Particular preference is given to cyclohexane-soluble alcoholates, such as potassium tert-butylamyl alcoholate, these being used in a lithium-potassium ratio which is preferably from 30:1 to 40:1. This method can simultaneously achieve a low proportion of 1,2-linkages of the butadiene units.
The proportion of 1,2-linkages of the butadiene units is preferably in the range from 8 to 15%, based on the entirety of 1,2-, 1,4-cis-, and 1,4-trans linkages.
The weight-average molar mass Mw of the copolymer block (S/B)A is generally in the range from 30 000 to 200 000 g/mol, preferably in the range from 50 000 to 100 000 g/mol.
Random copolymers (S/B)A can, however, also be produced via free-radical polymerization.
At room temperature, the blocks (S/B)A form a semi-hard phase in the molding composition, and this phase is responsible for the high ductility and tensile strain at break values, i.e. high elongation at low strain rate.
The glass transition temperature of the copolymer block (S/B)B is preferably in the range from −60 to −20° C. The glass transition temperature is affected by the comonomer constitution and comonomer distribution, and can be determined via differential scanning calorimetry (DSC) or differential thermal analysis (DTA), or can be calculated from the Fox equation. The glass transition temperature is generally determined using DSC to ISO 11357-2 with a heating rate of 20 K/min.
The copolymer block (S/B)B is preferably composed of from 30 to 50% by weight or styrene and from 50 to 70% by weight of butadiene.
Preference is given to block copolymers which comprise one or more copolymer blocks (S/B)B composed of vinylaromatic monomers and dienes with random distribution. These can by way of example be obtained via anionic polymerization using alkyllithium compounds in the presence of randomizers, such as tetrahydrofuran, or potassium salts. Preference is given to use of potassium salts, using a ratio of anionic initiator to potassium salt in the range from 25:1 to 60:1. This method can simultaneously achieve a low proportion of 1,2-linkages of the butadiene units.
The proportion of 1,2-linkages of the butadiene units is preferably in the range from 8 to 15%, based on the entirety of 1,2-, 1,4-cis-, and 1,4-trans linkages.
Random copolymers (S/B)B can, however, also be produced via free-radical polymerization.
The blocks B and/or (S/B)B forming a soft phase can be uniform over their entire length or can have division into differently constituted sections. Preference is given to sections having diene (B) and (S/B)B which can be combined in various sequences. Gradients are possible, having continuously changing monomer ratio, and the gradient here can begin with pure diene or with a high proportion of diene, with styrene proportion rising as far as 60%. A sequence of two or more gradient sections is also possible. Gradients can be generated by reducing or increasing the amount added of the randomizer. It is preferable to set a lithium-potassium ratio greater than 40:1 or, if tetrahydrofuran (THF) is used as randomizer, to use an amount of THF less than 0.25% by volume, based on the polymerization solvent. An alternative is simultaneous feed of diene and vinylaromatic compound at a slow rate, based on the polymerization rate, the monomer ratio being controlled here in accordance with the desired constitution profile along the soft block.
The weight-average molar mass Mw of the copolymer block (S/B)B is generally in the range from 50 000 to 100 000 g/mol, preferably in the range from 10 000 to 70 000 g/mol.
The proportion by weight of the entirety of all of the blocks S is in the range from 50 to 70% by weight, and the proportion by weight of the entirety of all of the blocks (S/B)A and (S/B)B is in the range from 30 to 50% by weight, based in each case on the block copolymer.
There is preferably a block S separating blocks (S/B)A and (S/B)B from one another.
The ratio by weight of the copolymer blocks (S/B)A to the copolymer blocks (S/B)B is preferably in the range from 80:20 to 50:50.
Preference is given to block copolymers having linear structures, in particular those having the block sequence S1-(S/B)A-S2-(S/B)B-S3 (tetrablock copolymers), where each of S1 and S2 is a block S.
These feature a high modulus of elasticity of from 1500 to 2000 MPa, high yield stress in the range from 35 to 42 MPa, and tensile strain at break above 30%, in mixtures using a proportion of more than 80% by weight of polystyrene. By way of comparison, commercial SBS block copolymers having this proportion of polystyrene have a tensile strain at break value of only from 3 to 30%.
Particular preference is given to tetrablock copolymers of the structure S1-(S/B)A-(S/B)B-S3, which comprise a block (S/B)A composed of from 70 to 75% by weight of styrene units and from 25 to 30% by weight of butadiene units and a block (S/B)B composed of from 30 to 50% by weight of styrene units and from 50 to 70% by weight of butadiene units. Glass transition temperatures can be determined using DSC, or calculated from the Gordon-Taylor equation, and for this constitution are in the range from 1 to 10° C. The proportion by weight of the entirety of the blocks S1 and S2, based on the tetrablock copolymer, is preferably from 50% to 67% by weight. The total molar mass is preferably in the range from 150 000 to 350 000 g/mol, particularly preferably in the range from 200 000 to 300 000 g/mol. Tensile strain at break values of up to 300% with a proportion of more than 85% of styrene can be achieved here by virtue of the molecular architecture.
Block copolymers which are composed of the blocks S, (S/B)A, and (S/B)B, for example tetrablock copolymers of the structure S1-(S/B)A-S/B)B-S3, form co-continuous morphology. Here, there are three different phases combined in one polymer molecule.
The soft phase formed from the (S/B)B blocks provides the impact resistance in the molding composition, and can prevent propagation of cracks (crazes). The semi-hard phase formed from the blocks (S/B)A is responsible for the high ductility and tensile strain at break values. Modulus of elasticity and yield stress can be adjusted by way of the proportion of the hard phase formed from the blocks S and optionally admixed polystyrene.
The block copolymers of the invention generally form highly transparent, nanodisperse, multiphase mixtures with standard polystyrene.
The block copolymer of the invention is a suitable component K1) in transparent molding compositions which are tough and stiff, using polystyrene as component K2) and optionally using a block copolymer K3) which differs from K1).
A preferred mixture is composed of the following components:
K1) from 20 to 95% by weight of a block copolymer A as described above, and
K2) from 5 to 80% by weight of standard polystyrene (GPPS) or impact-resistant polystyrene (HIPS), and
K3) from 0 to 50% by weight, preferably from 10 to 30% by weight, of a block copolymer B which differs from K1 and is composed of vinylaromatic monomers and dienes.
In molding compositions using this mixture, the block with glass transition temperature below −30° C. of components K3) forms the soft phase, and the hard phase is formed from at least two different domains, which are composed of polystyrene or, respectively, a polystyrene block and the block (S/B)A of the block copolymer of component K1).
Component K1)
The block copolymer described above of the invention is used as component K1).
Component K2)
A styrene polymer, preferably standard polystyrene (GPPS), or impact-resistant polystyrene (HIPS), is used as component K2). For maintaining transparency, particular preference is given to standard polystyrene in the form of oil-free or oil-containing variants. Examples of suitable standard polystyrenes are Polystyrene 158 K and Polystyrene 168 N from BASF SE, or the corresponding oil-containing variants
Polystyrene 143 E or Polystyrene 165 H. It is preferable to use from 10 to 70% by weight of relatively high-molecular-weight polystyrenes with weight-average molar mass Mw in the range from 220 000 to 500 000 g/mol, and it is particularly preferable to use from 20 to 40% by weight of these.
Component K3)
The component K3) used can be a block copolymer composed of vinylaromatic monomers and dienes, and differing from K1). It is preferable to use, as component K3), a styrene-butadiene block copolymer which has a block B with glass transition temperature below −30° C., acting as soft block.
The mixture of the invention preferably comprises from 5 to 45% by weight, particularly preferably from 20 to 40% by weight, of the block copolymer K3.
Suitable block copolymers K3) are in particular stiff block copolymers which are composed of from 60 to 90% by weight of vinylaromatic monomers and from 10 to 40% by weight of diene, based on the entire block polymer, and whose structure is mainly composed of hard blocks S comprising vinylaromatic monomers, in particular styrene, and of soft blocks B or S/B comprising dienes, such as butadiene and isoprene. Particular preference is given to block copolymers having from 65 to 85% by weight, particularly preferably from 70 to 80% by weight, of styrene and from 15 to 35% by weight, particularly preferably from 20 to 30% by weight, of diene.
The copolymer blocks (S/B)B of the block copolymer K3) preferably have random distribution of the vinylaromatic monomers and dienes.
Preferred block copolymers K3) have a star-shaped structure having at least two terminal hard blocks S1 and S2 with different molecular weight composed of vinylaromatic monomers, where the proportion of the entirety of the hard blocks S is at least 40% by weight, based on the entire block copolymer B. Linear structures are also possible, examples being (S/B)B-S2, or S1-(S/B)B-S2, or S1-(B->S)n.
The number-average molar mass Mn of the terminal blocks S1 is preferably in the range from 5 000 to 30 000 g/mol, and the number-average molar mass Mn of these blocks S2 is preferably in the range from 35 000 to 150 000 g/mol.
Preference is given to polymodal styrene-butadiene block copolymers having terminal styrene blocks, for example those described in DE-A 25 50 227 or EP-A 0 654 488.
Particular preference is given to block copolymers K3) having at least two blocks S1 and S2 composed of vinylaromatic monomers and having, between these, at least one random block (S/B)B composed of vinylaromatic monomers and dienes, where the proportion of the hard blocks is above 40% by weight, based on the entire block copolymer, and the 1,2-vinyl content in the soft block S/B is below 20%, for example those described in WO 00/58380.
The block copolymers K3) are commercially available, for example with the trademarks Styrolux® 3G 33/Styroclear® GH 62, Styrolux® 693 D, Styrolux® 684, Styrolux® 656 C, Styrolux® 3G55, K-Resin® 03, K-Resin® 04, K-Resin® 05, K-Resin® 10, K-Resin® KK38, K-Resin® 01, K-Resin® XK 40, Kraton® D 1401P, Finaclear 520, 530, 540, 550; Asaflex® 805, 810, 825, 835, 840, 845 Asaflex® product line, Clearen® 530 L, and 730 L.
Plasticizer
It is possible to use, as plasticizer E, from 0 to 6% by weight, preferably from 2 to 4% by weight, of a homogeneously miscible oil or oil mixture, in particular white oil, vegetable oils, or aliphatic esters, such as dioctyl adipate, or a mixture of these. Medicinal white oil is preferably used.
The mixtures of the invention are highly transparent and are particularly suitable for the production of foils, in particular of thermoforming foils for blister packs, and of containers or moldings for the packaging of electronic components, and in particular for extruded hollow profiles for integrated circuits (ICs). They are moreover suitable for the production of injection moldings which are tough and stiff.
Test Methods:
Glass transition temperatures were determined using Differential Scanning Calorimetry (DSC) to ISO 11357-2 with a heating rate of 20 K/min.
Molecular weights were determined using gel permeation chromatography (GPC) in tetrahydrofuran (THF) at 23° C., by means of UV detection, and evaluated by using polystyrene as standard.
Modulus of elasticity, yield stress, and tensile strain at break were determined to ISO 527.
Block Copolymers K1-1 to K1-5
For production of the linear styrene-butadiene block copolymers, 5385 ml of cyclohexane were used as initial charge in a 10 liter double-walled stirred stainless-steel autoclave with cross-blade stirrer, and titrated to the end point with 1.6 ml of sec-butyllithium (BuLi) at 60° C., until a yellow coloration appeared, brought about by 1,1-diphenylethylene used as indicator, and 3.33 ml of a 1.4 M sec-butyllithium solution were then admixed for initiation, and 0.55 ml of a 0.282 M potassium tert-amyl alcoholate (PTAA) solution was admixed as randomizer. The amount of styrene (420 g of styrene 1) necessary for the production of the first S block was then added and polymerized to completion. The further blocks were attached in accordance with the structure and constitution stated in table 1 via sequential addition of the appropriate amounts of styrene or styrene and butadiene, in each case with complete conversion. For production of the copolymer blocks, styrene and butadiene were added simultaneously in a plurality of portions, and the maximum temperature was limited to 77° C. by countercurrent cooling. For block copolymer K1-1, 84 g of butadiene 1 and 196 g of styrene 2 were used here for the block (S/B)A, 196 g of butadiene B2 and 84 g of styrene 4 were used for the block (S/B)A and 420 g of styrene 5 were used for the block S3.
The living polymer chains were then terminated via addition of 0.83 ml of isopropanol, and 1.0% of CO2/0.5% of water, based on solids, were used for acidification, and a stabilizer solution (0.2% of Sumilizer GS and 0.2% of Irganox 1010, based in each case on solids) was added. The cyclohexane was removed by evaporation in a vacuum oven.
Weight-average molar mass Mw for the block copolymers K1-1 to K1-7 is in each case 300 000 g/mol.
Mixtures M 1 to M 8
The parts by weight stated in table 2 of the block copolymers K1-3 and K1-4, and also of components K2 (Polystyrene 158 K) were mixed at from 200 to 230° C. in a 16 mm twin-screw extruder and pressed to give sheets. The mixing ratios and mechanical properties of the sheets are collated in table 2. Unless otherwise stated, the component stated in the top row was used.
| Number | Date | Country | Kind |
|---|---|---|---|
| 081727794 | Dec 2008 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2009/067012 | 12/14/2009 | WO | 00 | 6/23/2011 |
