NL8802127A - PRODUCTS CONSTRUCTED FROM COMPATIBLE POLYMER MIXTURES. - Google Patents

Description

/ N.0. 35266

Product made from polymers forming compatible polymer blends

Description 5

The invention relates to articles which are made up of polymers which form compatible polymer mixtures, namely an alkyl-substituted polystyrene as polymer component P1 and a carbonyl group-containing polymer component P2. One of the 10 polymers then forms a coating on the other polymer, respectively. a coating on the compatible polymer blends PM.

State of the art

As a rule, different polymer types are considered incompatible, i.e. different polymer types do not generally form a homogeneous phase to only minor amounts of a component, which would be characterized by complete miscibility of the components.

Certain exceptions to this rule have aroused particular interest in those skilled in the art of theoretical explanation of the phenomena. Fully compatible polymer blends exhibit complete solubility (miscibility) in all blend ratios.

A summary presentation on miscible polymer systems can be found, for example, at D.R. Paul et al. In Polymer and Engineering Science 18, (16) 1225-34 (1978); J. Macromol. Sci-Rev. Macromol. Chem.

C. 18 (1) 109-168 (1980) as well as in Annu. Rev. Mater. Sci., 1981, 299-319. The glass transition temperature Tg or the so-called "optical method" (transparency of a film cast from homogeneous solution of the polymer mixture) was often used to demonstrate the miscibility. (See Brandrup-Immergut, Polymer Handbook, 3rd part, II1-211-213) As a further test on the miscibility of mutually different polymers, the occurrence of the Lower Critical Solution Temperature (LCST) is used. (See DE-A- 3,436,476.5 and DE-A-3,436,477.3) The occurrence of the LCST is based on the process that when heated, the first transparent, homogeneous polymer solution is separated into phases and becomes opaque optically cloudy. clear evidence that the original polymer blend had consisted of a single, balanced homogeneous .0802127 4 2 nth phase For further characterization of blends see also the contribution of MT . Shaw: "Microscopy and Other Methods of Studying Blends" in "Polymer Blends and Mixtures", edited by D.J. Walsh, J.S. Higgins and A. Maconnachie, NATO ASI Series, Series E: Applied 5 Sciences No. 89, biz. 37-56, Martinus Nijhoff Publishers Dordrecht / Boston / Lancester 1985. Examples of miscibility present are, for example, the systems polyvinylidene fluoride with polymethyl methacrylate (PMMA) or with polyethyl methacrylate. (U.S. Patent Nos. 3,253,060, 3,458,391 and 3,459,843). Newer results on "Polymer Blends" and possible uses thereof are reported by L. M. Robeson in Polym. Engineering and Science 2 £ (8) 587-597 (1984) report.

Copolymers from styrene and maleic anhydride, as well as from styrene and acrylonitrile, are compatible under certain conditions with polymethyl-15 methacrylate (PMMA) (DE-A-2,024,940). Emphasis has been placed on the improved utilization properties of molding compositions of these types. Likewise, copolymers of styrene and hydrogen bondable monomers capable of hydrogen bonding are compatible with polymethacrylates at certain compositions, i.e., for example, copolymers of styrene and p- (2-hydroxyhexafluoroisopropyl) styrene (BY Min and Eli M. Pearce, Organic Coating and Plastics Chemistry 45, (1981) 58-64), or copolymers of styrene and allyl alcohol (F. Cange! Osi and MT Shaw, Polymer Preprints (Am. Chem. Soc. Div. Polym. Chem.) 24, (1983), 258-259).

Polystyrene itself as well as other polymers containing styrenes, on the other hand, are considered incompatible with polymethyl methacrylate. For example, Shaw, M.T. and Somani R.H. a miscibility of only 3.4 ppm (PMMA with a molecular weight of 160,000) resp. of 7.5 ppm (PMMA with a molecular weight of 75,000) indicated with polystyrene [Adv. Chem. Ser. 1984, 206 (Polym. Blends Compos. Multiphase Syst.), 33-42 (C.A. 101: 73417 e)]. Even very small molecular polystyrene is not very compatible with PMMA. For example, a mixture of 20¾ of an extremely small mol of ecular styrene oligomer (mol weight: 3100) no longer gives a transparent product. At a still very small molecular weight of 9,600, even a only 5 percent solution in PMMA is only transparent. (Raymond E. Parent and Edward V. Tompson, Journal of Polymer Science: Polymer Physics Edition, Vol. 16, 1829-1947 (1978)).

Similarly, other polymethacrylates and polyacrylates are miscible with polystyrene to form transparent plastics. This applies, for example, to polyethyl methacrylate, polybutyl methacrylate, polyisobutyl methacrylate, polyneopentyl methacrylate, polyhexyl methacrylate and many others. See also R.H. Somani and M.T. Shaw, Macromolecules 14, 1549-1554 (1981).

An exception to this generally observed incompatibility between poly (meth) acrylate and polystyrene is reported in two newer patent applications (P. 3,632,370.5 and P 3,632,369.1, not yet disclosed). Accordingly, polystyrene resp. poly-α-methylstyrene with polycyclohexyl methacrylate and polycyclohexyl acrylate extremely well compatible. The compatibility of poly-10-cyclohexyl (meth) acrylate with polystyrene and poly-α-methylstyrene is so good that compatibility between the styrene-containing polymer and the cyclohexyl (meth) acrylate-containing polymer is still present when cyclohexyl ( meth) acrylate to less than 50% by weight (e.g. 30% by weight) is present in the copolymer. Likewise, the polystyrene drawing can be replaced by other comonomers without losing compatibility between the styrene-containing polymer and the cyclohexyl (meth) acrylate-containing polymer.

In addition to this extraordinary, complete miscibility of cyclohexyl (meth) acrylate with polystyrene and poly-α-methylstyrene, a miscibility of polystyrene with only polyvinyl methyl ether, polyphenylene oxide and tetramethylene bisphenol-A polycarbonate is described (DR Paul and JW Barlow J Macromol Sci-Rev Macromol Chem C 18 (1) 109-168 (1980)).

The miscibility is usually explained by specific interactions between the different polymer types. For example, the above-mentioned compatible polymer blends (e.g., tetramethylbisphenol-A polycarbonate / polystyrene) are explained by electron donor acceptor complex formation (see JW Barlow and DR Paul, Annu. Rev. Mater. Sci., 1981, 299-319) .

However, most of the hitherto known compatible polymer blends are traced back to special hydrogen bond bond interactions (ie, for example, phenoxy / polyester, PVC / polyester, SAA / polyester, PC / PHFA, PVDF / PMMA, see JW

Barlow and D.R. Paul, Annu. Rev. Mater. Sci. 1981, 303, 304).

Thus, while the above-mentioned compatible polymer mixtures are traced back to hydrogen bond bonds or electron-donor-acceptor complex formation, the compatibility of PMMA with special copolymers of styrene and acrylonitrile or α-methylstyrene and acrylonitrile, which in each case are only used with a particular styrene, is explained / acrylo-40 nitrile or α-methylstyrene / acrylonitrile ratio is found, by c 8802127 * 4 * an intramolecular repulsion within the copolymer between the two comonomers styrene and acrylonitrile. This also makes it clear that compatibility (e.g. between PMMA and SAN) is found only for a very special composition of the copolymer. Since compatibility is found only at very special comonomer ratios, one speaks of "miscibility windows". (J.-L.G. Pfennig et al, Macromolecules 1985, 18, 1937-1940). Such "miscibility windows" are also reported in compatible mixtures of aliphatic polyesters and polyhydroxy ethers of bisphenol A. Here, the 10 aliphatic polyesters are considered to be copolymers of CHX and COO monomer building blocks. (D. R. Paul and J. W. Barlow, Polymer, 25, 487 (1984)). With this work, Paul and Barlow were able to demonstrate that exothermic miscibility as a miscibility driver can exist even if none of the interaction parameters are negative. Only a sufficient repulsion energy between the comonomers of the copolymer is required.

With this concept in mind, Gerrit ten Brinke et al. Also explain the miscibility of halogen-substituted styrene copolymers with poly (2,6-dimethyl-1,4-phenylene oxide) (Macromolecules 1983, 16, 20 1827-32) and Ougizawa and Inoue, Polym. J., 18> 521-527 (1986) the miscibility of poly (acrylonitrile-co-styrene) with poly (acrylonitrile-co-butadiene).

While, on the one hand, the compatibility of special copolymers with other polymers - as mentioned above - is explained by intramolecular repulsion within the copolymers and thus also the found "miscibility window", for the interpretation of the compatibility with homopolymers, special interactions are always used ( for example, EDA complexes in the case of polyphenylene oxide / polystyrene or hydrogen bonding bonds in the system PVDF / PMMA). Therefore, there is no self-contained theory of miscibility in the polymer that would allow the finding of new compatible polymer blends. However, such compatible polymer blends are sought for many applications.

For example, blends of polymers (polyblends) have in some cases and in certain areas of the plastics industry led to improved plastic products in terms of properties (see Kirk-Öthmer, 3rd Ed. Vol. 18, pp. 443-478, J. Wiley 1982). The physical properties of such "polyblends" usually represent a compromise that below the mark may represent an improvement over the properties 40 of the individual polymers. In addition, multi-phase polymer blends of many phases have acquired an unequally greater commercial significance than the compatible blends (see Kirk-Othmer loc. Cit.

449).

The present invention relates to articles which are composed of polymers which form compatible polymer mixtures, namely an alkyl-substituted polystyrene as polymer component PI and a carbonyl-containing polymer component P2, one of the polymers coating the other polymer resp. forms a coating on the compatible polymer blends PM.

The present invention is based on the following conditions, which are the subject of the basic application P 3.638.443.7.

Problem and solution

Multi-phase and compatible polymer mixtures must therefore be kept strictly apart in terms of their physical as well as their application-technical relevance, in particular their optical properties (transparency, transparency, etc.). As already mentioned, often inadequate compatibility of plastics blending with the aim of thereby achieving an improved total property spectrum places narrow limits. However, the prior art did not teach the finding of the compatible polymer blends required by the art.

It has been found that the concept of the rejection between the comonomer building blocks (for example, the rejection between styrene and acrylonitrile in SAN), prepared to explain the compatibility of copolymers, can be transferred to homopolymers and that rules for technical handling can be derived from this. distracted. The new teaching for understanding polymer blends therefore provides for miscibility between different polymers PI and P2, when: 1) Polymer PI is composed of monomer building blocks with at least two chemically distinct subunits that are mutually repellent, and 2) Polymer P2 also consists of monomer building blocks, which in turn again consist of at least two chemically distinct subunits, which are also mutually repelling, and 3) a negative or only slightly positive mixture enthalpy for the mixture of the hydrogenated polymer monomer building blocks 40 1 is measured with polymer 2.

.8802127 4 6 4

The teaching informally explains the miscibility between halogen-containing polymers on the one hand and carbonyl group-containing polymers on the other. As can be proven in other examples, mixtures of alcanes and perfluoroalkanes are generally endothermic. Thus, with PVDF in a monomer building block two subunits (the CH2 and the CFg groups) are united, which repel.

The PMMA is also composed of two repellent subunits, a hydrocarbon residue and an ester group.

The class of compatible polymers used according to the invention is a mixture of two types of polymer, the compatibility of which can be explained, for example, neither by hydrogen bonds nor by EDA complex formation.

A condition of the articles claimed according to the invention is therefore the finding that polymer mixtures PM from two different polymers P1 and P2 then have good compatibility when

Polymer PI is built up of polymers of the formula I or contains these monomers as the main constituent, wherein R1 for hydrogen or methyl and R2 for a hydrocarbon residue with 1 to 18, preferably 1 to 12, carbon atoms and polymer P2 is composed of monomers of formula 2 , or contains it as the main constituent, where R3 is for hydrogen, methyl or a group - (^ - X-CHgRg, X for a group 25 0 0 0

II II II

- C - Z -, - Z - C -, - Z - C - Z '- meaning Z = oxygen or NR4, 30 Z' = oxygen or NR4 and R4 = hydrogen or an alkyl radical with 1-12, at preferably 1 to 5 carbon atoms, -CHR 5 R 5 represents an aliphatic or araliphatic hydrocarbon radical having 5 to 24 hydrocarbon atoms, wherein Rg and Rg are either bonded to an optionally substituted ring with 5 to 12 carbon atoms in the ring, or R 5 is for hydrogen or an aliphatic hydrocarbon radical with 1-5 carbon atoms and Rg represents an optionally branched aliphatic, araliphatic or 40 aromatic hydrocarbon radical with 4-18 carbon atoms.

o 8802127 7

Preferably R2 also represents an aliphatic hydrocarbon radical. The optionally substituted radicals are inert substituents, for example n-alkyl, isoalkyl and tert-alkyl groups with 1-6 carbon atoms, for example methyl, ethyl, propyl, isopropyl, butyl, etc. (See also below. the R £ group is written as -CH3CR7R3, see page 11).

Of particular interest are those polymer mixtures PM from polymers 10 PI and polymers P2, which meet the additional condition that the Van der Waals volumes Vy of the

Rg group to the job: 15 (1) Vy. 1 »8> VM> 0.6. Vy -X-CHR5R6 -x-chr5r6, 20 meet.

In it, Vy stands for the Van der Waals volurne, -x-chr5r6 expressed in cmfymol, the -XCHRgRg group and Vw for the corresponding Van der Waals vol urn of the group. For the definition of the Van der Waald volumes, see A. Bondi, J. Phys. Chem. 68, 441 (1964); M. Charton in Topics in Current Chemistry, Vol. 114, Steric Effects in Drug Design, p. 107, Springer Verlag 1983 ....

Particular preference is given to those polymer mixtures PM which fulfill the condition: c8802127 _____ ____— ^ # 5 8 (2) Vyj. 1.5> Vy ^ 0.7. Vw meet.

-X-CHR5R6 “X-CHR5R6

Furthermore, those polymer mixtures PM are preferred which satisfy the condition that the hydrogenated (saturated) monomer building blocks of the polymer PI H1 (compound of formula 3) and the hydrogenated monomer building blocks of the polymer P2 H2 (compound of formula 4) not more than a slightly positive mixture enthalpy (ie mixture H1 / H2 <50 cal / mol mixture) or preferably a negative mixture enthalpy, so that: AH mixture H1 / H2 <0 cal / mol mixture applies.

15

As a rule, this exothermic mixture of the hydrogenated building blocks and thus also the miscibility of the polymers PI and P2 is caused by a repulsion within the monomer building blocks of the polymer PI and within the monomer building blocks of the polymer P2, as initially caused example PVDP / PMMA resp. PVC / PMMA has been proposed.

In addition, the repulsion within the monomer building block of polymer P2 relies on the aforementioned repulsion between the polar X group and the aliphatic -CHgCRs group as well as the -CHRsRg group.

On the other hand, the repulsion within the monomer building block of the polymer PI relies on the repulsion between aliphatic and aromatic hydrocarbons. As a general rule, it applies as a rule that a compatibility of polymer PI and polymer P2 in particular exists when the repulsion forces within the monomer building blocks are particularly great. A good miscibility between the polymers P1 and P2 is therefore particularly found when the aliphatic moiety present in the main chain, which directly adjoins the phenylene group in the monomer building block of the polymer Pi and in the monomer building block of the polar group X, as pronounced as possible. Therefore, as a rule, a better compatibility with the polymers P2 is found for polymers with R1 = CH3 than for polymers where R1 is hydrogen. This is especially true for a small Rg residue. (R2 = C1-C4).

Completely analogously, a particularly good compatibility with the polymers PI is also found within the group of the polymers P2, "8802127 when R3 is CH3. Furthermore, it is advantageous if the group -CHR5R5 forms a self-contained, compact hydrocarbon residue, in which as a rule care must be taken that the group X-CHR5R5 is adapted to the 5 -R2-qr ° ep in its place requirement. (ie comparable Van der Waals volumes from 10 groups are present). While with large substituents R2 (for example R2> 4 carbon atoms) a plurality of substituents -CHRgRg is eligible, as long as the CHRgRg residue contains only at least 5 carbon atoms, especially with a small R2 ** residue (for example R2 = CH3) CHRsRg radicals of the cycloaliphatic 15 or phenylalkyl radicals type are preferred.

The R2 group can in principle be placed at the o-, m- or p-position on the phenyl radical. Preferred, however, is the m or p position and very particularly the p position.

The f1 radical - as mentioned - represents either hydrogen, methyl het-20 or a group of -CH-X-CHR5R6. Preferred are R3 radicals with R3 = hydrogen or methyl. Within the -CH-X-CHRgRg residues, those with the structure -CH-C-Z-n 0 are preferred.

Group X is of type 30 0 00

II II II

-C-Z-, -Z-C- or -Z-C-Z, where 35 groups are 0 0

II II

-C-Z- and -Z-C-40, 880212? <10 are preferred and particular priority is given to the group 0 i -C-Z-.

In principle -Z- can be oxygen or a group -NR4- with R4 = hydrogen or an alkyl radical, in particular with 1 to 5 carbon atoms. Very generally preferred is oxygen or a 10 -NR4 group with R4 = hydrogen. Very particular preference is however given to -Z groups, in which -Z- is oxygen.

As already mentioned, the group -CHR5R6 should be adapted appropriately to the —R2 ~ res-t in terms of its space requirements (Van der Waals volume). Of particular interest are -CHRgRg radicals in which R5 and Rg are closed to form a cycloaliphatic radical. These include rings with 5-12 carbon atoms in the ring. Preferred are 5-7 carbon atoms in the ring and most particularly cyclohexyl radicals, in which the ring may also be substituted in each case. Again, the above-mentioned approximation applies: in the case where R 1 is hydrogen and R 2 does not contain quaternary carbon atoms (= a carbon atom surrounded by 4 carbon atoms), the cycloalkyl moiety should not be doubly substituted for a carbon atom of the ring ie in this case the CHRgRg residue should also not contain any quaternary carbon. Conversely, especially when the R2 moiety contains a quaternary carbon, the CHRgRg moiety may also contain a quaternary carbon, in this case even such CHRgRg moieties are preferred, wherein at least one carbon atom of the CHRgRg moiety is preferred. - generally a carbon atom of the Rg moiety - is substituted with at most one hydrogen atom. As a rule, Rg will be hydrogen or form a ring with Rg. In addition, however, R5 can also represent an alkyl radical with 1 to 5 carbon atoms.

If it is considered that the polymer P1 is essentially a building monomer of the formula I, then all alkyl-substituted styrenes and / or α-methylstyrenes, in particular those R2 radicals can be mentioned, wherein R2 represents an 18802127 611 CH3CR7R8 residue, where R7 represents hydrogen or an alkyl radical of 1-8 carbon atoms and Rg represents an alkyl radical of 1-8 carbon atoms.

R2 radicals in which R7 and R8 are methyl are particularly preferred. In addition, R2 can also be methyl, ethyl or n-propyl.

The content of monomers of formula I of polymers PI depends on the degree of compatibility required and is at least 30% by weight, usually at least 60% by weight, preferably at least 10% by weight. Particular preference is given to those polymers PI with at least 95% by weight content of monomers of the formula 1. In the case where R 1 is H, homopolymers PI of the monomers of the formula 1 are the most particularly preferred embodiment.

Comonomers for the construction of the polymer PI in case comonomers are present at least are particularly suitable (from 1 different) vinyl monomers. (See Ullmann's EncyclopSdie der Technischen Chemie, 3rd edition, 14th part, p.

108-109, Urban und Schwarzenberg 1963). Monomers which are only built up from the elements carbon, hydrogen and oxygen are preferred. In particular these are vinyl esters and / or (meth) -acrylic acid esters, in particular those with 4-22 carbon atoms in the molecule. Styrene or α-methylstyrene may also be present in the polymer in minor amounts, i.e. in amounts up to less than 20% by weight.

Thus, while the polymer PI can be modified with other hydrophobic vinyl compounds, the content of highly polar monomers such as, for example, acrylamide, acrylonitrile 1, maleic anhydride, maleic imides, p- (2-hydroxyhexafluoroisopropyl) styrene or allyl alcohol is very limited. The content of these polar monomers should be below 10 wt.%, Resp. be below 5 wt% of the polymer PI. Particular preference is given to those polymers A which contain less than 0.1% by weight of these polar monomers, especially those which do not contain polar monomers.

The content of the monomers of formula II of polymers P2 also depends on the degree of compatibility required and is at least 30% by weight, usually at least 50% by weight, preferably at least 70% by weight and in a particularly preferred embodiment,> 95 wt%. Of particular interest for many applications is the use of homopolymers of the monomers of formula II 40 for the construction of the polymers P2.

.8802127 j 12

In addition to the monomers of the formula II, the monomers mentioned for the polymer PI are suitable as comonomers for the construction of the monomer P2, the use of highly polar monomers also being limited here (as a rule, polar monomers up to a content of 20 wt%, preferably <5 wt% limited, if not entirely excluded).

The monomers of the formula II, which build up the polymer P2 substantially {> 50% by weight) - if not even up to 100% - are the vinyl esters, vinyl amides, vinyl carbonates, vinyl urethanes and vinyl ureas which can be derived from formula 2, as well as the corresponding propenyl compounds. In addition, the monomers of formula II represent amides and ester of itaconic acid. Preferred monomers of formula II, however, are esters and amides of acrylic acid and of methacrylic acid. Very generally, as already mentioned, the esters are particularly preferred. In the case where nitrogen-containing monomers of formula II are used, those without NH group are preferred. Special ones should be mentioned as monomers of formula 2: optionally substituted vinyl or propenyl esters of cycloalkane carboxylic acids and cycloalkyl carbonates, cycloalkyl acrylic atoms, cycloalkyl-20 methacrylates and cycloalkylitaconates, optionally substituted vinyl esters or propenyl esters of phenylalkylcarboxylic acids, phenylalkylcarboxylic acids , methacrylates and itaconates. Particularly mentioned are cyelohexyl acrylate and cyclohexyl methacrylate. However, it must always be ensured that the monomers of the formula II of the polymer PI and the monomers of the formula 2 of the polymer P2 cannot be seen in isolation.

For example, the divestiture of the subunits of the monomer building block 1 and the spatial expansion (Van der Waals volume) of the subunits of the monomer building block 1 in relation to a divestment of the subunits of the monomer building block 2 and their spatial expansion must always be seen.

For example, poly-p-tert-butyl styrene (as polymer PI) has a pronounced sterically demanding portion (the tert-butyl group) directly adjacent to the phenylene group. The pronounced repulsion between the aliphatic and the aromatic part of this monomer unit present therewith makes poly-p-tert-butylstyrene an ideal mixture partner for polymer P2, the only limitation being that polymer P2 also serves a pronounced repulsion within the monomer building block. ie, in addition to the polar group X, a large (best even branched) aliphatic residue -CHRgRg.

.8802127 13 t

Thus, therefore, poly-p-tert-butylstyrene (polymer PI) is also unlimitedly compatible with the sterically demanding poly-3,3,5-trimethylcyclobexyl acrylate (above said mixture, range 1:99 to 99: 1).

Complete compatibility is found throughout the experimentally accessible temperature range (i.e., up to> 250 ° C) with this polymer blend PM.

As an example of a polymer mixture PM according to the invention with unlimited compatibility, polymer PI and polymer P2 with the units of formulas 5 and 6 are mentioned, respectively. Unlike poly-10-p-tert-butylstyrene as polymer PI, poly-p-methylstyrene does not exhibit pronounced aliphatic regions adjacent to the phenylene group, i.e. the group repulsion within the monomer building block is considerably less. As a result, the variation width within the polymer P2 is also smaller. Consequently, poly-p-methylstyrene is completely incompatible with the above-mentioned poly-3,3,5-trimethylcyclohexyl acrylate.

Full compatibility, on the other hand, is found with polycyclohexyl acrylate as polymer P2. (Poly-p-methylstyrene and polycyclohexyl acrylate both have no quaternary C atoms in the alkyl radical and are similar in geometry). On the other hand, the non-sterically demanding polymer P2 already exhibits an excellent compatibility of poly-p-tert-butylstyrene as polymer PI with the sterically less demanding, poly-cyclohexyl acrylate as polymer P2, which has a considerably smaller volume, as the polymer P2, already clearly reduced. Although these polymers are still fully compatible at room temperature, demixing occurs upon heating to about 80 ° C.

Example of a polymer mixture according to the invention with unlimited compatibility: Polymer PI with the units of formula 7 and polymer P2 with the units of formula 8.

In addition to these polymer mixtures which are compatible in the total temperature range and in all mixing ratios, polymer mixtures PM are also important, which are only compatible in a limited temperature range (for instance <100 ° C). As a rule, the mixing ratio of polymer PI to polymer P2 can be varied within wide limits. Thus, the polymer mixtures PM according to the invention generally consist of: A) 0.1 - 99.9, preferably 5 to 95% by weight of a polymer PI, which consists of at least 30% by weight of the monomers of the formula 1 is built-40 and 8802127 κ 14 s Β) 99.1-0.1, preferably 95 to 5 wt% of a polymer P2, which is at least 30 wt% of the monomers of formula 2 .

It also depends on the technical application requirements whether polymer PI can also contain monomers of formula 2 or polymer P2 also monomers of formula 1. As a rule, it can be the case that the content of the monomers of formula 1 in polymer PI has at least 30% by weight should be higher than the content of the monomers of formula 1 in polymer P2. Similarly, the monomers of formula 2 in polymer P2 should be at least 30% by weight higher than the monomers of formula 2 in polymer PI. Particular preference is given to those polymer mixtures in which the content of monomers of formula 1 in polymer P2 <10 wt.%, Very particularly preferably 0 wt.%, And the content of monomers of formula 2 in polymer PI also <10 wt. %, very particularly preferably 0% by weight.

In general, it holds that the content of monomers of formula 1 in polymer PI and the content of polymers of formula 2 in polymer P2 can be especially low when the remaining monomer building blocks in polymer PI and in polymer P2 chemically similar.

The characterization of the monomer mixtures PM according to the invention as compatible mixtures takes place according to the recognized criteria {see Kirk-Othmer, loc. Cit., Vol. 18, pp. 457-460).

A) When optical processes are used, polymer mixtures PM according to the invention observe a single refractive index which lies between that of the two polymer components P1 and P2.

b) The polymer blends PM have a single glass transition temperature Tg (which is between that of the polymer components).

For further characterization of the polymer mixtures PM according to the invention see also the above contribution of M.T. Shaw in "Polymer Blends and Mixtures." 35 The compatibility criteria outlined above are also significant for the use according to the invention of the polymers P2 as a coating agent for the polymers PI.

The present invention, as mentioned, relates to articles of the compatible polymer blends PM with a coating of polymer P2.

.8802127 15

Preparation of the polymers PI and P2

The polymers P1 and P2 can be prepared according to the known rules of polymerization and according to known methods. The PI type polymers can be prepared, for example, according to Houben-Weyl, 5 Methods of Organic Chemistry, 4th Edition, Vol. XIV / I, pp. 761-841, George Thierne-Verag (1961); some are also commercially available in suitable form. Preferably, the polymerization process with radicals, but also ionic polymerization processes, can be used. The molecular weights M of the polymers PI used according to the invention are generally above 3000, preferably in the range from 5,000 to 1,000,000, particularly preferably in the range from 20,000 to 500,000 (determination by light scattering). In the meantime, it should be emphasized that the molecular weights do not appear to critically influence the suitability as a component in the compatible polymer blends PM 15. This applies to both the homo- and the copolymers of the types PI and P2. The tacticity of the polymers is of particular significance for the compatibility of polymer PI and polymer P2. As a rule, in particular, a polymer P2 with a low content of isotactic triads (such as it is obtained by radical polymerization, for example), is preferred over polymers with a high isotactic content, such as is produced by special ionic polymerization. The preparation of the gay resp. copolymers P2 usually takes place by polymerization with radicals. (See H. Rauch-Puntigam, Th. Völker, Acryl- und Methacryl-25 Verbundungen, Springer-Verlag 1967). When in principle (for example with acrylic acid or methacrylic acid derivatives) a preparation by anionic polymerization or polymerization with transfer of groups is also possible (see also OW Webster et al., J. Am. Chem. Soc., 105, 5706 (1983)) However, the preferred preparation form is still the polymerization with radicals.

The molecular weights M of the polymers P2 are generally above 3000, generally in the range of 10,000 to 1,000,000, preferably 20,000 to 300,000. When choosing the monomer components to be used as comonomers at P2, care should be taken that the glass transition temperature Tg of the resulting polymer does not affect the technical utility of the total system PM. For the preparation of molded articles, at least one of the polymers P1 and P2 must have a glass transition temperature Tg> 70 ° C; for this application is preferable,

40 that the polymer mixture PM also has a glass transition temperature Tg> 70 ° C

.880 * 127 Μ 16 'i.

possession. This limitation preferably applies to the preparation of injection-molded, pressed or. extruded articles. However, for other fields of application, for example for lacquers, those polymer mixtures PM are preferred, which have a polymer component P2 with a glass transition temperature Tg <40 ° C or preferably 20 ° C.

The compatibility of the polymer blends PM makes the corresponding technical application possibilities plausible, whereby PI resp. P2 in each case deputizing for the polymers PI or.

10 P2 options covered are listed.

1. By encapsulating PI with P2, it is possible to produce an optical gradient fiber, for example with the following configuration: core: PI, jacket P2, transition: as a rule, n ^ Opi> n20p2 is continuous.

Such fibers can, for example, be used as light guide cables.

2. Products of PI with a thin jacket of P2, in particular of P2 with a (copolymerized) UV absorber, are also accessible. See R. Gchter, H. Mllller, Taschenbuch der Kunststoff-Additive, Hanser-Verlag 1979, pp. 90-143; GB-A-2,146,647; US-A-4,612,358). Unlike non-enveloped PI, such articles are resistant to weathering. The otherwise serious problem of the re-use of heterogeneous coated plastic waste is eliminated, because waste can be processed again due to its good compatibility. As a rule, the products of PI or. manufactured from the polymer mixture PM by spraying, pressing, extruding, rolling or casting. The polymer P2 jacket is usually applied by lacquering or by coextruding.

3. PI plates with P2 cladding can be manufactured. Plates with such a structure have a 2% improved light transmission compared to untreated PI plates.

As a rule, plates with P2 coating also have better scratch resistance and altered corrosion resistance. The emphasis here is also on the good adhesion of the polymer P2 to the PI plates. In particular, this allows the manufacture from plates PI with a coating from P2 by coextrusion. Particularly interesting are multiple connecting plates, 8802127 f, 17, as they are used, for example, for glazing greenhouses, which are made of PI or a polymer mixture P and have a coating of P2.

Furthermore, cleavages of molded articles from PI with polymer P2 or advantageously with monomer 2 containing monomer / initiator mixtures can be performed. Here, the high polymerization rate of the monomer 2 (especially in the case of R3 = H) can be combined with the good polymer compatibility.

The following examples will illustrate the invention without limiting it.

The determination of the reduced viscosity (T ^ spec / c) is based on DIN 1342, DIN 51562 and DIN 7745. The determination of the light transmittance can be carried out according to DIN 5036, unless stated otherwise. The haze (haze) is indicated in% (ASTM D 1003). The measurements are generally carried out on a 3 mm thick plate 20. The proportions indicated refer to weight ratios.

Examples

Example I

A 3 mm thick poly-p-methylstyrene plate (J = 83 ml / g) is mixed with a 20% solution of a polymer P2 in a solvent mixture of 40% by weight diacetone alcohol 30 40% by weight 2-propanol 20 weight 5 methyl ethyl ketone coated and then dried at 90 ° C. Characterization of the polymer P2: Radolymers copolymer prepared with the composition 49 wt% methyl methacrylate, 49 wt% cyclohexyl-35 methacrylate, 2 wt% cyclohexyl acrylate (J = 32 ml / g).

A crystal clear plate with a well-adhering coating results.

Example II

40 An approximately 10 µm thick coating of polycyclohexyl methacrylate (J = 31 ral / g) is applied to a 1 mm thick plate of poly-p-methylstyrene (J = 83 ml / g) "880212.7 * 18. The coated plate thus obtained is milled, granulated and extruded into a 1 mm thick plate again (simulation of reprocessing waste).

The plates thus obtained, like the pure poly-p-methylstyrene plates, are crystal clear.

.8802127

Claims (4)

1. Articles composed of polymers, which form compatible polymer mixtures of two polymer components, characterized in that a) the polymer components A) are a polymer PI, consisting of at least 30% by weight of monomers of the formula 1, wherein for hydrogen or methyl and R2 represents a hydrocarbon radical having 1-18 carbon atoms, and B) a polymer P2, which contains at least 30% by weight of monomers of formula II, wherein R3 represents hydrogen, methyl or a group II II -CH2-X-CHR5R6, X for a group -CZ-, -ZC-, 15 0 II, ZC-Z'-, 20 where Z = oxygen or -NR4, Z '= oxygen or NR4, and R4 = hydrogen or an alkyl radical with 1-12 carbon atoms, -CHR5R6 represents an aliphatic or araliphatic hydrocarbon radical with 5-24 carbon atoms is built up, imagine that the articles are formed such that one of the 25 polymers has a coating on the other or 3) one of the polymers on a compatible polymer blend forms PM A) 0.1-99.9 wt% of a polymer PI and B) 99.1-0.1 wt% of a polymer P2 forms a coating. Articles according to claim 1, characterized in that PI and P2 form an optical gradient fiber. Articles according to claim 1, characterized in that the polymer P2 forms a coating on the polymer PI. Articles of manufacture according to claim 1, characterized in that the polymer P2 contains an agent for the protection against light. > 8802127