CA1332038C - Compatible polymer mixtures - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The present invention relates to a molded object comprising a first molded polymer P1 coated with a second polymer P2. Polymer P1 comprises at least 30% by weight of monomers having Formula I:

(I) wherein R1 is hydrogen or methyl, R2 is a hydrocarbon group containing 1-18 carbon atoms, the polymer P1 containing less than 20 weight%
styrene or .alpha.-methyl styrene. Polymer P2 comprises at least 30% by weight of monomers having Formula II:

Description

- l- 1332038 This application is a division of Canadian patent application Serial No. 551,531 filed November 10, 1987, which relates to compatible polymer mixtures (polymer blends) of an alkyl-substituted polystyrene as polymer component Pland a polymer component P2 which contains carbonyl groups.
As a rule, different polymer species are considered to be incompatible with on~ another, i.e. different polymer species generally do not form a homogeneous phase, which would be characterized by complete miscibility of the components, even down to slight amounts of a component.
Certain exceptions from this rule have caused increasing interest, particularly among the -~
experts concerned with the theoretical ~ ;
interpretation of the phenomena. Completely compatible mixtures of polymers demonstrate complete solubility (miscibility) in all mixture ratios.

.~;

~.;
~, ,,'~.

i332038 A summary representation of miscible polymer systems can be found, for example, in D.R. Paul et al.
in Polymer & Engineering Science 18 (16) 1225 - 34 (1978); J. Macromol. Sci.-Rev. Macromol. Chem. C. lS
(1) 109 - 168 (1980) as well as in Annu. Rev. Mater.
Sci., 1981, 299 - 31g. ;~
As evidence o the miscibility, the glass temperature Tg or the so-called "optical method"
(clarity of a film poured from a homogeneous solution _0 of the polymer mixture) is often used as a reference.
(See Brandrup-Immergut, Polymer Handbook, 2nd edition, III, 211-213.) As a further test for the miscibility of pclymers which are di~ferent from one another, the occurrence of the lower critical solution temperature (LCST) is used. (See DE-A 34 36 476.5 and DE-A
34 36 477.3). The occurrence of the LCST is based on ~;
the process which occurs during ~7arming, where the ~;
` polymer mixture, which has been clear and homogeneous until then, separates into phases and becomes optically cloudy to opaque. This behavior is a clear indication, ;:~
according to the litèrature, that the original polymer mixture had consisted of a single homogeneous phase which was in equilibrium. For a further ~,.
characterization of blends see also the contribution by M.T. Shaw: "Microscopy and Other Methods of Studying Blends" in Polymer Blends and Mixtures edited by D.J.

Walsh, J.S. Higgins and A. Maconachie, NATO ASI
Series, Series E: - Applied Sciences-No. 89, p. 37-56, Martinus Nijhoff Publishers, Dordrecht/Boston/-Lancester 1985. Examples of existing miscibility are represented, for example, by the systems polyvinylidene fluoride with polymethyl methacrylate ~PMMA) or with polyethyl methacrylate, (U.S.
3,253,060, U.S. 3,458,391, U.S. 3,459,843). Recent results concerning "polymer blends" and possible applications for them are reported by L.M. Robeson -~
in Polym. Engineering & Science 24 (8) 587 - 597 -~
(1984).
Copolymers of styrene and maleic acid anhydride, as well as of styrene and acrylonitrile are compatible with polymethyl methacrylate (PMMA) under certain conditions (DE-A 20 24 940). The improved usage properties of molding masses of ~-these types was emphasized. In the same way, copolymers of styrene and monomers which contain ~;;
hydroxyl groups which can form hydrogen bonds with a certain composition are also compatible with polymethacrylates, for example copolymers of styrene and p-(2-hydroxylhexafluoroisopropyl) styrene (B.Y. Min and Eli M. Pearce, Organic Coating and Plastics Chemistry, 45, (1981) 58 - --~
64), or copolymers of styrene and allyl alcohol (F. Cangelosi and M.T. Shaw, Polymer Preprints (Am Chem. Soc. Div. Polym. Chem.) 24, (1983), 258 - -~

,~

;'~-`

~- _4_ ~` 1332038 259). Polystyrene itself as well as other polymers which contain styrene are considered to be incompatible with polymethyl methacrylate. For example, M.T. Shaw and R.H. Somani indicate a miscibility with polystyrene of only 3.4 ppm (PMMA with a molecular weight of 160,000) or 7.5 ppm (PMMA with a molecul~r weight of 75,000). See Adv. Chem. Ser. 1984, 206; Polym. Blends Compos. Multiphase Syst., 33 - 4~, (CA 101 : 73 417e). Even polystyrene with a very low molecular io weight has little compatibility with PMMA. For example, a mixture of 20~i of a styrene oligomer with~an extremely low molecular weight (MW : 3,100) still does not yield a clear product. At a molecular weight of : :
9,600, which is also still very low, even a solution of only 5% in PMMA is just translucent. (Raymond R. -, Parent and Edward V. Tompson, Journal of Polymer Science: Polymer Physics Edition, Vol. 16, 1829 - 1947 , ~ (1978)). ~
, ~ ... i Other polymethacrylates and polyacrylates -demonstrate just as little miscibility with polystyrene to form transparent plastics. This is true, e.g., for ~-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 e~ception to this generally observed incompatibility between poly(meth)acrylate and polystyrene is reported in two recent patent applications ~P 36 32 370.5 and P 36 32 369.1).
According to this, polystyrene and poly-a-methyl styrene are extremely compatible with polycyclohe~yl methacrylate and polycyclohexyl acrylate. The compatibility of polycyclohexyl (meth)acrylate with polystyrene and poly-~-methyl styrene is so good that compatibility between the polymer which contains styrene and the polymer which contains cyclohexyl -(meth)acrylate still exists if the cyclohexyl (meth)acrylate is contained at less than 50% by weight (or example, 30% by weight) in the copolymer. In the same way, the styrene can be extensively replaced by other comonomers, without the compatibility between the polymer which contains styrene and the polymer which contains cyclohexyl (meth)acrylate being lost.
Aside from this extraordinary, complete miscibility of cyclohexyl (meth)acrylate with polystyrene and poly-~-methyl styrene, miscibility of polystyrene is only reported with polyvinyl methyl ether, polyphenylene oxide and tetramethyl bisphenol-A- -~
polycarbonate (D.R. Paul and J.W. Barlow, J. Macromol. ;
Sci.-Rev. ~acromol. Chem., C 18 (1), 109 - 168 (1980)). The miscibillty is generally explained by . .

specific interactions between the different polymer species. The compatible polymer mixtures mentioned above (e.g. tetramethyl bisphenol-A-polycarbonate/polystyrene) are explained by electron donator-acceptor complex formation, for example. (See J.W. Barlow and D.R. Paul, Annu. Rev. Mater. Sci., 1981 299 - 319).
- The majority of the compatible polymer mixtures known until now, however, are attributed to special interactions of the hydrogen bond formation type (for example, phenoxy/polyester, PVC/polyester, i~`
SAA/polyester, PC/PHFA, PVDF/PMMA. See J.W. Barlow and -;
D.R. Paul, Annu. Rev. Mater. Sci., 1981, 303, 304).
The compatible polymer mixtures mentioned above ;
are attributed to hydrogen bond formation or to ;
electron donator-acceptor complex formation. The compatibility of PMMA with special copolymers of styrene and acrylonitrile or ~-methyl styrene and acrylonitrile, which is found only at a certain styrene/acrylonitrile or ~-methyl styrene/acrylonitrile `~
ratio in each case, is explained by an intramolecular ; repulsion within the copolymer between the two comonomers styrene and acrylonitrile. This also makes it understandable that compatibility (for example between P~MA and SAN) is found only for a very specific composition of the copolymer. Since compatibility is _7_ only found for very specific comonomer ratios, this is termed "miscibility willdows" (J.-L.G. Pfennig et al., Macromolecules 1985, 18, 1937 - 1940). Such "miscibility windows" are also reported for compatible mixtures of aliphatic polyesters and polyhydro.Yy ethers of bisphenol A. Here, the aliphatic polyesters are viewed as copolymers of CHx- and COO-monomer modules.
(D.R. Paul and J.W. Barlow, Polymer, 2S, 487 (1984)).
Paul and Barlow were able to show with this study that 0 an exothermic miscibility can exist as a driving force for miscibility even if none of the interaction parameters are negative. The only requirement is sufficiently great repulsion energy between the comonomers of the copolymer.
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, 18Z7 - 32) with precisely this concept, and Ougizawa and Inoue, Polym. J., 18, 521 - 527 (1986) use it to explain the miscibility of poly(acrylonitrile co-styrene) with poly(acrylonitrile co-butadieneJ.
While on the one hand, the compatibility of specific copolymers with other polymers is therefore ;~
explained by intramolecular repulsion within the copolymers, thereby also explaining the "miscibility `'; ':.''.
,, ~1332038 windows," specific interactions are always referred to for an interpretation of the compatibility of homopolymers (e.g. EDA comple~es in the case of polyphenylene oxide/polystyrene or hydrogen bond formation in the system PVD~/PMMA). There is no overall theory to explain miscibility in a polymer t which can be used to find new compatible polymer ;
mixtures. Such compatible polymer mixtures are sought for many applications, however.
Mechanical mixtures of polymers (polyblends) have resulted in plastic products with improved properties in certain cases and in-certain areas of the plastics industry (See Kirk-Othmer 3rd edition, Vol. 18, pp. 443 - 478, J. Wiley 1982). The physical properties of such "polyblends" generally represent a compromise, which can mean an overall improvement as compared with the properties of the individual polymers. In these ..
situations, multi-phase polymer mixtures have achieved much yreater commercial significance than compatible mixtures (See Kirk-Othmer, loc. cit., p. 449.) Multi-phase and compatible mixtures must thereEore be kept strictly separate with regard to both their -~
physical properties and their properties which are relevant for application technology, especially their optical properties (transparency, clarity, etc.). As `
already explained, a lack of compatibility often sets ~332038 ~-.

narrow limits for mixing plastics with the goal of thereby achieving an improved overall spectrum of properties. However, the state of the art does not offer any teaching to assist in finding the compatible polymer mixtures demanded by technology.
The compatible polymer mixtures proposed in ~;
the parent application are compatible in all proportions and at all useful temperatures. They also exhibit de-mixing upon heating as well as reduced water absorption, double refraction, refractive index and improved processing properties.
The compatible polymer mixtures according to ~ -the invention of the parent application comprise:
a miscible polymer mixture of A) 0.1-99.9% by weight of a polymer P1 which comprises at least 30% by weight of monomers ~ ~
having Formula I: ~ ' Rl ' . '' CH2 = C (I) wherein R1 is hydrogen or methyl and R2 is a `;
hydrocarbon group with 1 - 18 carbon atoms, wherein polymer P1 contains less than 20 weight%
styrene or a-methyl styrene; and ! . ' .~ ~

~ ~ . ! . . . _ .. . . . ..

- lO- 1332038 B) 99-0.1% by weight of a polymer P2 which comprises at least 30% by weight of monomers ~3 IH2 = C (II) wherein R3 is hydrogen, methyl or a group -CH2-X-CHRsR6, X is a groupO O O
-~-Z-, -Z-~, -Z-C-Z'-, where Z is oxygen or -NR~, Z' is oxygen or NR4, and R4 is hydrogen or an alkyl group with 1 - 12 carbon atoms, and -CHRsR6 is an aliphatic or araliphatic hydrocarbon group with 5 - 24 carbon atoms.
The present divisional application is directed to a molded object comprising a first molded polymer Pl coated with a second polymer P2, wherein polymers P1 and P2 are as defined above. 1 The molded object of this invention can be a film, plate, sheet, fiber or cable and it can be :
produced by injection, pressing, extrusion, rolling or casting.
A more complete appreciation of the invention and many of the attended advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed ;~
description when considered in connection with the accompanying drawings, wherein~

~ I 3 !3 2 0 3 8 Figure 1 illustrates the heat of mixing of perfluoro-n-hexane and n-hexane.
Figure 2 illustrates the heat of mixing of perfluorocyclohexane and 1,3,5-trimethylcyclo-hexane;
Figure 3 illustrates the heat of mixing ofdecalin and acetic acid ester;
Figure 4 illustrates the heat of mixing of 3-pentanone and n-heptane; ,~
Figure 5 illustrates the quantity of heat -developed when mixing acetic acid ester with cyclohexane;
Figure 6 illustrates the heat of mixing of acetone and chloroform; and Figure 7 illustrates the heat of mixing of N~
hexane and benzene. ~
It is particularly unsatisfactory that the ; -interpretation of the polymer mixtures known until now, i.e. in particular the type of assumed specific interactions, such as the assumption of hydrogen bonds between PVDF and PMMA, in other words hydrogen bonds proceeding from the -CH2-CF2-group of the PVDF to the ester group of the PMMA
is in contradiction to any experience. The same is true for the hydrogen bonds between PVC and PMMA which are cited so frequently. The present invention makes use of the realization that ;~
.

''.
.
.. , :

`~ -12- 1332038 such assumptions (such as hydrogen bonds between PVDF and PMMA or between PVC and PMMA), which contradict experience, are not at all necessary for an understanding of the miscibility of these polymers. Rather, it has been found that the concept of repulsion between the comonomer modules (e.g. repulsion between styrene and acrylonitrile in SAN) can be transferred to homopolymers and that rules for technical action can be derived from it.
The new theory for an understanding of polymer mixtures therefore provides miscibility between different types of polymers Pl and P2 if:
1) polymer Pl is composed of monomer modules with at least two subunits which can be chemically differentiated, which repulse each other; and 2) polymer P2 also consists of monomer modules which in turn are composed of at least two subunits which can be chemically differentiated, which also repulse each other, and 3) a negative or only slightly positive enthalpy of mixing for the mixture of the hydrogenated monomer modules of polymer Pl with polymer P2 is measured.

X

~` - 13 - I 3 3 2 0 3 8'' ., , ", The new theory explains the miscibility ~;~
between polymers which contain halogens, on the one hand, and polymers which contain carbonyl groups, on the other hand, without difficulty, which will be demonstrated in the following. The ;
data required for this can be obtained from ~ -~
general tabular compilations, such as Landoldt-Borstein, 5th and 6th edition, Berlin, Julius- ;
Springer-Verlag. Figure 1 shows the heat of mixing of perfluorohexane and hexane. As is evident from Figure 1, this mixture is strongly endothermic; ~H mixture for an equimolar mixture is + 500 cal/mol of mixture. The corresponding mixture of perfluorocyclohexane and cyclohexane is just as strongly endothermic (see Figure 2). As can be documented with further examples, mixtures of alkanes and perfluoroalkanes are generally endothermic. Therefore, in the case of PVDF, ;
there are two subunits combined in one monomer module ~the CH2 and the CF2 groups which repulse each other.
In the same way, PMMA is also composed of two subunits which repulse each other, a hydrocarbon portion and an ester group.
Figure 3 shows the heat of mixing of acetic acid ethyl ester and decaline (288 cal/mol of ;~
mixture), Figure 4 shows the heat or mixing of pentanone (3) and n-heptane. Here again, a distinct repulsion between ! . , ;

-the carbonyl groups and alkane can be seen. In Figure 5, the repulsion between the aliphate [cyc1Ohexane) and carbonyl group is represented as a temperature change during mixing. As can be seen, the repulsion increases with an increasing content of carbonyl groups in the ester. Correspondingly, clearly distinct cooling ;
occurs during mixing. According to this, the compatibility of PVDF and PMMA can be understood as a direct consequence of the repulsion between the CH2 and CF2 subunits of the PVDF as well as the repulsion between the aliphatic part and the ester group of the ~-PMMA. The compatibility of PVC with PMMA can be interpreted in a completely analogous way. For example, the mixture of chloroform and cyclohexane is endothermic (165 cal/mol of mixture for a 1 mix~ure). In contrast, the mixture 1,1,2,2,~
tetrachloroethane/acetic acid ethyl ester which corresponds to the polymer mixture PVC/PMMA is strongly exothermic (- 608 cal/mol of mixture for a 1 : 1 mixture). The mixture of chloroform/acetone, which is ~;
shown in Figure 6, is also exothermic. The new way of ;~
interpreting the miscibility of PVD~/PMMA and ~ hydrocarbons which contain chlorine and PMMA is a ;~ direct consequence of the surprising discovery of a ;
whole class of compatible polymers, which could not have been explainedl not to mention predicted, with the '''`'''' .

~15- 13320:3~ -rules and criteria of the prior art. The new class of polymers according to the invention involves a mixture of two polymer species whose compatibility cannot be explained either by hydrogen bonds or by EDA comple.Y
formation. ~
It was now found that surprisingly, polymer :
mixtures PM of two different polymers ~1 and P2 demonstrate good compatibility if polymer 1 tPl) is composed of monomers with Formula I or contains these monomers as a major component 1~1 :".
~ ` `~
~2 :
';':

where Rl stands for hydrogen or methyl and R2 stands for a hydrocarbon group with 1 - 18, preferably 1 - 12 carbon atoms and polymer P2 is com?osed of monomers wlth ~ormula II or contains these as a major component CH2 = C II
;-CHR5R6 ~

_15_ wher~ ~3 ~t~ o~ hydroqen, m~thyl or a group C~2 X - C~5R6~ X st~nda for a group O o - o -- C -- Z --,-- z -- C --,-- Z -- C -- Z

where Z is o o~ NR4, Z' 1~ 0 or ~4 ~nd R~ is hydroaen or an alkyl group with 1 - 12, preferably 1 - 5 carbo~ -atcms, -C~R5R6 stands or an aliphatic or ar~ hatic hydrocarbon group with 5 - 31 carbon atoms, with R5 and R6 eithPr being connected ln a rin~, t~ form an optionally substltuted ~ing with 5 - 12 carbon ~to~s, or ~5 at~nd~ ~or hydrog~n a~d ~n aliph~ti~. hy~rnc3rbon group and ~6 ~tand~ ~or an opt~onally ~ubstituted ~llphatic, araliphatlc o~ a~omatic hydrocarbon gro~p, with ~ - 18 carhon ~oms. Pre~era~ly, ~2 al~o ~tand~
Eor an allphatic hydrocarbon group. The optionally 3ubstituted ~roups invol~Je inert substituents, for example n-alkyl, iso-alkyl and ter~. alkyl group~ with :~
1 - 6 car~on a~oms, e.g~ methyl, ethyl, propyl, i~opropyl, butyl, etc. ~he R2 group may also be a .;~
~ -C~3R7R~ group as discussed below.
: 20 ~ho~e pbl~m~ mixtures PM o~ polymers rl ~nd .i~;
:~ . pol~mers P2 whlch fulfill the add~t1onal ~equirement that t~ Van der W~ olu~eg (Vw) of th~

group satisfy the relation ~1~ V~ . 1,8 ~ Vw Q ~ ~ ~ Yw --X-C~R~Rh ~ .R2 -X-C~R~6 ~.
~, ~ , '.;

/ -17 -~

~332038 find partieul~r int.~res~. Ther~ ~Y_Y_C~R R~ stands ~or the Va~ der Waal~ ~olume, expressed in c.~/mol, of the -X-cHR5~6 ~roup~ and Vw _ ~ 2 -stand~ ~or the co~responding Van der '~aal~ volume o~
the ~ R2 group. For a de~in~tion ~ the ~dl~ der W~ volumcc~ ;~
see A. Bondi, J. Phys. Chem. 68, 441 (1964~; M. Charton .
in ~opicr in ~ rren~ Ghçmistsy~ Yol, 114, Steric ~:
Effects in Drug ~e~ign, p. 107, Springe~ Verla$ 1983.
~hose polymer m~.ture5 PM which satisfy the ~e~uirement ~;

~) V~ . 1,5 ~ VW ~
-X-C~R5n6 ~ ~2 -X-CHnsR6 , Ar~ ~art~ ~ularlY preferred.
Furth~ Le~ tho-~ poly~er ~ixture~ P~ ~hich satisfy the requirement that the hydrogenated (saturated) monomer modules of the polyme~ P1 -18~

~Rl ~ ~2 and the hydrogenated monomer modules of the ~
polymer P2 -demonstrate at most a slightly positive enthalpy -~
of mixing (i.e. ~ H mixture H1/H2 < 50 cal/mol of mixture, or preferably a negative enthalpy of mixing, so that the following applies:
H mixture H1/H2 < 0 cal/mol of mixture.
As a rule, this exothermic mixing of the , . . :;~
hydrogenated monomer modules and thereby also the miscibility of the polymers P1 and P2 is caused by ~`
repulsion within the monomer modules of the polymer P1 and within the monomer modules of the ~1 polymer P2, as this was shown initially using the ;~
examples of PVDF/PMMA and PVC/PMMA.
Here, the repulsion within the monomer module of the polymer P2 is based on the repulsion, as ~;~
explained above, between the polar X group and the aliphatic -CH2-CR3 group as well as the -CHRsR6 group. See Figure 3 for an example of these .
repulsion forces.

,~' ' , ~, ~ - l9 - 1832038 In contrast, the repulsion within the monomer module of the polymer Pl is based on the repulsion between aliphatic and aromatic hydrocarbons.
Figure 7 shows the heat of mixing of n-hexane and benzene as an example. Here, the general rule applies that compatibility of polymer P1 and polymer P2 exists particularly if the repulsion forces within the monomer modules are especially great. Therefore, good miscibility between the polymer is particularly found if the aliphatic section found in the main chain, which is directly adjacent to the phenylene group in the monomer module of the polymer P1 and to the polar group X
in the monomer module is as distinct as possible.
This means that as a rule, better compatibility with the polymers P2 is found in polymers with R
is CH3 than in polymers where R1 is hydrogen.
This is particularly true for a small R2 group.
R2 is preferably C1 - C4. Completely analogously, particularly good compatibility with the polymers P1 is also found within the group of polymers P2 if R3 = CH3. ~-Furthermore, it is advantageous if the group -CHRsR6 forms a tightly packed compact ; 25 hydrocarbon and as a rule, attention should be paid to having the group X-CHRsR6 adapted to the ~ R

in ter~s of its space requirement (i.e. comparable Van der Waals volumes of the groups present).
While a large number of substituents -CHR5R6 is possible for large substituents R2 ~e.g. R2 ~ 4 carbon atoms), as long as the -C~R5R6 group has only at least 5 carbon atoms, cycloaliphatic CH5R6 or phenyl alkyl ;
group are preferred particularly in the case o~ a small R2-group (e.g. Rz is CH3).
The ~2 group can be localized, in principle, in .0 the o, m or p position at the phenyl group. However, the m or p position, and very particularly, the p position, is preferred.
;~ The R3 group representsj, as explained above, either hydrogen, methyl or a group of the type -CH2-X-CHR5R6. R3 groups with R3 is hydrogen or methyl are preferred. Within the -CH2-X-CHR5R6 group, those ~;
with the structure -CH2-C-Z- are preferred.
O . :~

O O o 11 11 11 ,~
The group X is of the type -C-Z-, -Z-C- OR -Z~C-Z, with the groups of the type ~
O O O ' Il 11 11 '~' -C-Z- AND -Z-C- being preferred and the group -C-Z-being particularly preferred. ~`

r ~ ~ 2 1-- 1 3 3 2 0 3 8 In principle, -Z- can be o:cygen or a -NR4- group with R4 is hydrogen or an alkyl group. In general, -Z- is oxygen or a -NR4- group with R4 not hydrogen. However, -Z- groups in which -Z- is oxygen are very especiall~
preferred.
It is preferred if the group -CHR5R6 is be adapted to the ~ ~2 group in terms of the space it takes `
up (Van der WaaLs volume). -C~R5R6 groups in which R5 and R6 are closed into a cycloaliphatic ring find particular interest. Here, rings with 5 - 12 carbon atoms in the ring should be taken into consideration.
Rings with 5 - 7 carbon atoms in the ring, and very especially cyclohexyl groups are preferred, and the ring can also be substituted in each case. Her~ again, the reciprocal adaptation mentioned above also applies: in case Rl is hydrogen and R2 does not contain any quarternary carbons the cycloalkyl group should not be doubly substituted at a ring carbon atom, i.e. in this case the CHR5R6 should not have any quarternary car~on, either. Vice versa, :he CHR5R6 i~ group can contain a quarternary carbon, particularly if the R2 group contains a quarternary carbon. In this case, those CHR5R6 groups in which at least 1 carbon atom of the CHR5R6 group - generally 1 carbon atom of the R6-group - is substituted with at most 1 hydrogen , -~ -~2- 133203~

atom. As a rule, R5 is hydrogen or forms a ring with R6. ~eyond this, however, R5 can also represent an alkyl group with 1 - 5 carbon atoms.
I we consider the monomer of Formula I which essentially comprises the polymer Pl, all alkyl-substituted styrenes and/or ~-methyl styrenes come into consideration, as a rule, with those R2 groups in which ~-R2 stands for a CCH3R7R8 group, with R7 standin5 for i hydrogen or an alkyl group with 1 - 8 carbon atoms and R8 standing for an alkyl group with 1 - 8 carbon atoms being particularly mentioned. ~`~
Those R2 groups in which R7 and R8 stand for methyl are especially preferred. In addition, R2 can also be methyl, ethyl or n-propyl.
The content of monomers o~ Formula I ln the polymers P1 depends on the extent of required compatibility and is at least 30% by weight, generally 60% by weight, preferably at least 80% by weight.
Those polymers Pl with a content of at least 95'~ by weight of monomers with Formula I are especially preferred. For the case that Rl is H, homopolymers Pl from the monomers of Formula I are the very especially preferred embodiment. -, As comonomers for the composition of the polymer Pl in which copolymers are present, vinyl monomers (different Erom Formula I) are particularly ~j '' . ~, ~ .. .. . . .. . ... . . ., ., . . ~ . . , , . --" ,," ", " ,,, ~ , ",.,,, ".. , ",.. ,,, ,""~ .,.. ,.. ~.,~,,~ ~.. i ".

~ 23-preferred. (5ee Ullmann's Encyclopadie der Technischen Chemie, 3rd edition, 14th Volume, p. 108 - 109, Urban &
Schwarzenberg 1963. Here, monomers which are composed only of carbon, hydrogen and o~ygen are preferred.
Especially, these are vinyl esters and/or (meth)acrylic acid esters, generally those with 4 - 22 carbon atoms ~-~
in the molecule. In subordinate proportions, i.e. in proportions of less than 20% by weight, styrene or ~-methyl styrene can also be contained in the polymer.
O While the polymer P1 can accordingly be modified with other hydrophobic vinyl compounds, the proportion of highly polar monomers, such as e.g. acrylamide, acrylonitrile, maleic acid a~hydride, maleic acid imides, p-(2-hydroxyhexaEluoroisopropyl) styrene or allyl alcohol is very limited. The proportion of these polar monomers should amount to less than 10% by weight or less than 5% by weight of the polymer Pl. Such polymers A which contain less than 0.1~ by weight of these polar monomers are especially preferred.
The content of monomers II in the polymers P2 is ~; also guided by the extent of required compatibility and ~-is!also at least 30% by weight, generally 50% by weight, preferably at least 70% by weight, and in an ;~
especially preferred embodiment, ~ 95% by weight. For ;~
many application purposes, the use of homopolymers of the monomers II to make up the polymers P2 is very particularly interesting.

~"

~332038 As comonomers for the composition of the polymer P2, the monomers identified above for the polymer P1 also come into consideration, in addition to the monomers with Formula II, with the use of highly polar monomers being limited here, also (as a rule, polar monomers are limited to a content of < 20~ by weight, preferably < 5~ by weight).
For the monomers of Formula II, which basically comprise the polymer P2 (> 50~ by weight) - if not actually 100% - preferred are the vinyl esters, vinyl amides, vinyl carbonates, vinyl urethanes and vinyl ureas which can be derived from Formula II, as well as the corresponding propylene compounds. In addition, the monomers of Formula II stand for amides and esters of itaconic acid. Preferred monomers II, however, are esters and amides of acrylic acid and ~
methacrylic acid. Very generally the esters are '' especially preferred. In case monomers with ;
Formula II which contain nitrogen are used, those without an NH group are preferred. The following should be particularly mentioned as monomers of Formula II: optionally substituted vinyl or propenyl esters, of cycloalkane carboxylic acids and cycloalkyl carbonates, cycloalkyl acryiates, ~;
cycloalkyl methacrylates and cycloalkyl ;~
itaconates, optionally substituted vinyl esters or propenyl esters, of phenylalkyl carboxylic acids and ,, .' ,~ .

,-, X ',,''~'~

.- -25- 1332038 phenylalkyl carbonates, phenylalkyl acrylates, methacrylates and itaconates. Cyclohe~yl acrylate and cyclohexyl methacrylate should be especiall~
mentioned. However, it should always be noted that the monomers of ~ormula II of the polymer Pl and the monomers of ~ormula II of the polymer P2 cannot be seen in isolation.
Therefore, the repulsion of the subunits of the monomer module I and the space occupied (Van der Waals volume) by the subunits of the monomer module I must always be seen in relation to a repulsion of the subunits of the monomer module II and the space it -occupies. ..
For example, poly-p-tert.-butyl styrene (as polymer Pl) demonstrates a distinct, sterically demanding aliphatic portion (the t-butyl group) risht next to the phenylene group. The distinct repulsion between the aliphatic and the aromatic part of this monomer unit which exists as a result makes poly-p-tert.-butyl styrene an ideal mixing partner for polymer P2, with the only restriction being that polymer P2 , i should also demonstrate a distinct repulsion within the -monomer module, i.e. in addition to the X group, a large (best of all, even a branched) aliphatic group .. . .. ~ . ... . . . . . . .

/ ~ -26-/
Accordingly, poly-p~tert.-butyl styrene ~polymer P1) is also ~o~patible, withou~ limita~ion, witih the ~teric~lly ~ n~ing poly-3rlr5~tri~ethyl c,~clohe~yl ~crylaite ~uv~ t~ mlx~ure r~n~e ~f 1 . ~ 5~ s indicated). In the polym~r mixturc P~, com~l~t~
compatibillty ls found in the entire temperature range accessible experi.~entally ~i.e. up to ~ 2SO~C~. .'' ~s an example of the polymer mixture P.~ with .
~nli~ited ccm~atibili~y accordinq to the ~ve~cion, the following are listed:
P~lymer Pl Po~.~m~r P~ ,h ~hP ~Ini t~

- C.;~ C~2 ~

~3 - I - C~3 ~ -:
C~3 ~ C-~3 :
C~3 C~3 In the examples give below, the excellent compatibility of poly-p-tert-butyl s~yrene as th~ polym~r Pl w1th the polymers P2 e demonstrated, with poly-p-tert-butyl styrene as ~;;
the ~odel system fo~ six fu~ther ex~mples.
In contrast to poly-p-tert-butyl ~ityrane a~ the l -poly~er 21, poly-?-methyl stlrene does not have any distinct aliphatic areas aside fro~ the phenylene 20 gr~up~ i.e. the repulsion of the qroup within the ... ,j", ~ .,, .~ " "~, ,.. ,,," ,1,~ . "~, ~,, , j' '" ~ - " . ~ " ,~

_~ -27- l332038 monomer module is significantly less. This also makes the range of variation within the polymer P2 less.
Accordingly, poly-p-methyl styrene is completely incompatible with the poly-3,3,5-trimethyl cyclohexyl acrylate mentioned above. Complete compatibility, on the other hand, is found with polycyclohexyl acrylate ;
as polymer P2. (Poly-p-methyl styrene and polycyclohexyl acrylate both have no quarternary carbon atoms in the alkyl group and are comparable in their geometry.) Compared with this, poly-p-tert-butyl styrene, which demonstrates excellent compatibility with sterically demanding polymers P2, as polymer Pl, demonstrates clearly lesser compatibility with the sterically less demanding polycyclohexyl acrylate which has a clearly lesser Van der Waals volume, as polymer ;~
P2. Although these polymers are still completely compatible at room temperature, de-mixing occurs when they are heated to approximately 80C.
An example for a polymer mixture with unlimited compatibility according to the invention:
Polymer PI Polymer P2 with the units o '' ~
~3 ~ `~

In addition to these polymer mixtures which are compatible over the entire temperature range and in all mixture ratios, those polymer mixtures PM which are only compatible in a limited temperature range (e.g. <
100C) are also interesting.
As a rule, the mixture ratio of polymer Pl and polymer P2 can be varied within wide limits.
Therefore, the polymer mixtures PM according to the invention generally consis$ of:
A) 0.1 - 99.9% by weight of a polymer Pl, which is composed by at least 30% by weight of monomers with the Formula I and ;~
:
~ B) 99.1 - 0.1% by weight of a polymer P2, which ,-, is composed by at least 30% by weight of monomers with Formula II.
Those polymer mixtures which consist of 1 - 99% by ~-weight of polymers Pl and 99 - 1% by weight of polymers P2 are primarily of interest. Those polymer mixtures which consist of 10 - 90% by weight of polymer Pl and ;~
90 - 10% by weight of polymer P2 are especially interesting. Finally, those polymer mixtures which consist of 20 - 80~ by weight of polymer Pl and 80 -_~ 23 ~332038 20% by weight of polymer P2 are very especially interesting. In each case, the composition of the polymer mixture PM is dependent on the technical requirements (see below).
It is also dependent on the technical requirements whether polymer Pl can also contain monomers of Formula II or polymer P2 can also contain monomers of Formula I. As a rule, it is true that the content of monomers -- of Formula I in the polymer Pl should be at least 30 by weight higher than the content of the monomers of Formula I in the polymer P2. Analogously, the content of monomers of Formula II in the polymer P2 should be at least 30% by weight higher than the content of monomers of Formula II in the polymer Pl. Those polymer mixtures in which the content of monomers of Formula I in the polymer P2 is < 10~ by weight, very especially preferably 0~ by weight, and the content of monomers of Formula II in the polymer Pl is also ~ 10%
by weight, very especially preferably 0% by weight, are especially preferred. In general, it holds true that the content of monomers of Formula I in the polymer Pl and the content o polymers of Formula II in the polymer P2 can be low, particularly if the other ~-monomer modules in the polymer Pl and in the polymer P2 ~-extensively agree in their chemistry.

~','', -- ~30- l1332038 The characterization of the polyrner mi:ctures Pl~
according to the invention as compatible miY.tures takes place according to the recognized criteria (see Kirk-Othmer, loc. cit., Vol. I8, pp. 457 - 460).
a) When using optical methods, a single index of refraction is observed in the polymer mixtures PM aceording to the invention, which lies between those of the two polymer components Pl and P2.
io b) The polymer mixtures PM possess a single glass transition temperature Tg which lies between that of the polymer components. ;~
For further characterization of the polymer mixtures PM
according to the invention, see the contribution by ~-~
M.T. Shaw in "Polymer Blends and Mi~tures" mentioned above.

Production of Polymers Pl and P2 . .

Production of the polymers Pl and P2 can take place according to the known rules of polymerization and according to known methods. The polymers of type Pl can be produced, for example, according to Houben-~leyl, Methoden der Organischen Chemie, 4th edition, Volume XIV/1, pp. 761 - 841, Georg Thieme Verlag (1961). Some of them are also commercially available in a suitable form. Preferably, the radical ~
;;

polymerization method can be used, but ionic polymerization methods can also be used. The molecular weights M of the polymers Pl used according to the invention are generally above 3,000, preferably in a range of 5,000 - 1,000,000, especially preferably in a -~
range of 20,000 - 500,000 (determination by light scattering). It should be emphasized, however, that the molecular weights do not appear to have any critical influence on the suitability as a component in the compatible polymer mixtures P~. This is true both ;~
~or the homopolymers and the copolymers of types Pl and ~-P2. For sood compatibility of polymer Pl and polymer P2, the tacticity of the polymers has a certain ~`
significance. As a rule, a polymer P2 with a low proportion of isotactic triads tsuch as one obtained by ~
radical polymerization, for example) is preferred over -polymers with a high isotactic proportion, such as one ~ .
produced by specific ionic polymerization. ;~
~.
The production of the homopolymers and/or ;`~
copolymers P2 is generally ca.ried out by radical -polymerization. (See H. Rauch-Puntigam, Th. Volker, Acryl- und Methacrylverbindungen, Springer-Verlag ;
1967). Even though production by anionic polymerization or group-transfer polymerization is possible in principle (see also O.W. Webster et al., J.
Am. Chem. Soc. 105t 5706 (1983)), the preferred form of production is radical polymerization.
'~;

: 32 The molecular weights M of the polymers P2 are generally above 3,000, in a general range of 10,000 to 1,000,000, preferably 20,000 to 300,000. ~or the selection of the monomer components which are to be used as comonomers or P2, care should be taken that the glass temperature Tg oE the resulting polymer does not have a restrictive influence on the technical applicability of the total system PM.
For the production of molded elements made from the polymer mixture PM, for example, at least one of the polymers Pl and P2 should demonstrate a glass ~
temperature Tg > 70C. It is preferred for this ~;:
application that the polymer -ixture PM has a glass :
temperature Tg > 70C. This restriction applies ~;-preEerably for the production o~ injection-molded, pressed or extruded objects made of the polymer mixture P~. Por other areas of application, for example for varnishes, for elastomers or or reversible thermotropic glazing (polymer mixture with clouding -point when heated), in other words for an application ;;~
in accordance with DE-A 34 36 477.3, however, those ~ polylmer mixtures PM are preferred which have a polymer ;
: component P2 with a glass temperature Tg < 40C or preferably < 20C.

13~2038 Production of the mixtures PM

The compatible mi:~tures P~ can be produced by ;
various methods. ~or example, they are produced by intensive mechanical mixing of the componerts Pl and P2 in the melt, in the extruder, etc.; or they can be produced out of a common solvent, as so-called "solution cast polyblends" (see Kirk-Othmer, "Encyclopedia of Chemical Technology", 3rd edition, Vol. 18, p. 443 - 478, J. Wiley, 1982). The method of procedure can also be that polymers Pl are dissolved in the monomer mixture of the other polymer P2 and subsequently produced in the presence of the polymer P2. Likewise, the polymer mixture PM can be produced out of common precipitants. There are no restrictions -~
on the type of mixing. A very good summary of the production of compatible polymer mixtures i5 given by M.T. Shaw, pages 57 - 67, "Polymer Blends and Mixture", noted above. Generally, mixtures of components Pl and P2 are produced first, with the starting materials most advantageously being solids, for example in the form of a bead polymer or a granulate, using slowly operating mixing systems such as drum, Rohn wheel, double chamber-plowshare mixers, or similar equipment. The slowly operating mixing systems cause mechanical mixing without eliminating the phase borders. (See Ullmann's Encyclopadie der Technischen Chemie, 4th edition, ~34~ ~332038 Volume 2, p. 282 - 311, Verlag Chemie.) Subsequently, thermoplastic treatment takes place, by homogeneous mixing in the melt, using mixing systems which can be heated at the temperatures suited for this, e.g. 150 to approximately 300C, in kneaders or preferably extruders, e.g. single-screw or multiple-screw extruders, or, if necessary, in extruders with an oscillating screw and shear pins te.g. in the BUSSCO kneader). Using this method, uniform grain granulates (e.g. hot deposit, cube shape, round grain) can be produced.
The grain size of the granulates is in a range from 2 to 5 mm. A further simple method for producing polymer mixtures PM is mixing polymer dispersions which contain the polymer component P1 and polymer dispersions which contain the polymer component B.
These dispersion mixtures can be coagulated together, spray-dried together or squeezed off together on an extruder. -Advantageous effects of the mixtures PM

The compatible polymer mixtures PM according to the invention especially demonstrate the following advantages, which imply the corresponding technical application possibilities with P1 and P2 each being listed to represent the possibilities in the category of polymers P1 and P2, respectively.

X~ .. ' 1. First, the polymer mixtures - in contrast to mixtures of other polymiers P1 which contain carbonyl groups and other polystyrenes - are ~-compatible. That is, the polymer mixtures PM
according to the invention are clear as glass in the non-pigmented state, in contrast to non-compatible polymer mixtures (they demonstrate no light scatering, i.e. as a rule, the haze is < 10%. However, those mixtures which are only compatible at room temperature, but demonstrate de-mixing when the temperature is increased, are also in accordance with the invention.
2. ~ixtures of P1 and P2, like polystyrene itself, demonstrate a low degree of water absorption.
3. Double refraction of the polymers P1 can ,~
be reduced by mixing with P2. The two aforementioned properties qualify the polymer mixtures PM for use especially as data storage ;~
material, particularly for information carriers which can be read optically. See J.Hennig, Kunststoffe 75, p. 425 (1985). -4. The refractive index of the polomer P1 can also be reduced, as a rule, by mixing with P2.
For example, the refractive index of P1 can be changed in such a way by mixing with P2 that the index of refraction of the polymer mixture PM can be adapted to the index of refraction of an -;~
embedded rubber phase. In this way, transparent, -~
impact-resistant plastics can be obtained.

.~, :'''''""":''"''" ''", ' ' ' ' ` '' ' ;' , ` ' ' " ' '' ' -36- ~332038 Polymer compositions which contain up to approximately 40 - 99% by weight, preferabl~ 70 - 95%
by weight of the pol~mer mi:cture P~l and 60 - 1o by weight, preferably 30 - 5~O by weight of an additionaL
polymer P3, difEerent from Pl and P2, are also particularly interesting; in these cases, it holds true that polymer P3 is incompatible with polymer Pl, P2 and with the mixture P~. As a rule, the composition of the polymer mixture PM is selected in such a way, in this case, that the inde~ of refraction of polymer P3 agrees with the inde~ of refraction of the mixture PM, generally, therefore, the following should apply at room temperature:
¦nD25pM - nD25p3¦ < O.01 As a rule, the polymer P3, which is incompatible with PM, will have a Tg < 20~C and will be covalently bonded with at least one of the components of the polymer mixture PM, in other words with Pl or P2, at least partially. In addition, the polymer P3 can be crosslinked. The case that the polymer P3 is polybutadiene or polyisoprene is very especially preferred.
Polymer compositions composed of 40 - 99~ by weight PM and 1 - 60~ by weight P3 are characterized by an improved impact resistance as compared with pure P~
particularly if P3 demonstrates a Tg < 20C.

```` 1332038 In particular, polymer compositions of 40 -9~ by weight PM and 60-1% by weight P3 allow a simple impact resistant mixture of polymers P2.

5. By sheathing P1 with P2, the production of an optical gradient fiber is possible, for example with the following configuration:
Core: P1, mantle: P2, transition: continuous As a rule, nD20P1 > nD2P2. Such fibers can be used as light conducting cables, for example.

6. Objects made of P1 with a thin mantle of P2, particularly of P2 with a W absorber (polymerized into it*), are also possible. In contrast to unsheathed P1, such objects are resistant to weathering. The problem of re-use of ;
heterogeneously coated plastic wastes, which is a serious problem otherwise, is eliminated, since wastes can be worked in again, because of the good compatibility. As a rule, the objects made of P1 or of the polymer mixture PM are produced by injection, pressing, extrusion, rolling or casting.
The mantle of polymer P2 is generally applied by varnishing or by coextrusion. `~

7. Plates of P1 with a coating of P2 can be produced. Plates with such a structure have a light permeability which is up to 2% improved as compared with plates of P1. As a rule, plates with a coating of P2 also demonstrate greater scratch resistance and a .,, ' ~,''-, :.
.;"""
* See US-A 4,576,870. --~

, ,-:

13~2038 changed corrosion resistance. Multiple skin sheets such as those used for glazing greenhouses, which have been produced from P1 or a polymer mixture PM and have a coating of P2, are particularly interesting.
Furthermore, cementation of molded elements of P1 with the polymer P2, or advantageously, with monomers/initiator mixtures which contain monomers II can be carried out. Here, the high polymerization velocity of the monomers II
(particularly in the case where R3 is H) can be combined with the good polymer compatibility. -~

8. Advantages with regard to processing technology result when using mixtures PM of > 90%
by weight P1 and < 10% by weight P2. In this case, the P2 takes over the functions of a processing auxiliary agent. This is particularly interesting for polymers P1 where R1 is methyl.

9. From the polymer mixtures PM according to the invention, transparent molded elements can be obtained, which have been modified at the surface by the action of energy, e.g. suitable radiation, in such à way that the polymer P1, where R1 is CH3, has been degraded but the polymer P2, where R3 is hydrogen, has not, for example, molded elements with a reflection-reducing surface and resists. In the same way, reflection-reducing molded elements can be produced by the fact ' ` ~ , ' ~ i:

that R1 is H and R3 is CH3. In this case, the polymer P2 can be degraded by the effect of energy.

10. The polymer mixtures PM according to the invention which demonstrate only limited compatibility find particular interest. Such compatible polymer mixtures which gain the capacity to scatter light when they are heated above the LCST can be advantageously used according to DE-A 34 36 476.5 for the presentation of information which can be read optically, or according to DE-A 34 36-477.3 for the construction of glazing systems with temperature-controlled transparency. The difference in the refractive index of polymer P1 and polymer P2, which is generally quite high, and the great light scattering which occurs in the case of de-mixing, as well as the broad possibility of variation in the values Rl, R2, R3, Rs, R6 and X make the 20 polymer mixtures PM according to the invention ~' particularly suitable for this area of -application. (See also the example poly-p-tert.- ,~
butyl styrene~polycyclohexyl acrylate.) -~
The following examples are intended to explain the invention, without limiting it. In particular, the large range of compatibility of the polymers P1 with the polymers P2 which contain `
carbonyl groups will be shown, particularly using ;~
the example of poly-p-tert-butyl styrene, which can be viewed as a typical '.' ~ ' :
'~

representative of the polymer species P1 (distinct aliphatic group directly next to the phenyl group), as polymer P1 (polymer P1 with R1 is H and R2 is tert-butyl).
On the other hand, using the example of poly-p-methyl styrene, which represents the limit of the range of validity of this invention as polymer P1 where R2 is methyl (polystyrene: R2 is hydrogen, and is not included in the present 10 invention), the limit of the invention will also -be shown. It should be specifically pointed out once again that specifically the borderline areas of compatibility (see Point 10 above) can be of particular interest from the point of view of application technology.
Determination of the reduced viscosity (~spec/c) is based on DIN 1342, DIN 51563 and DIN
7745. Determination of the light permeability can be carried out according to DIN 5036, unless otherwise specified. The cloudiness (haze) is indicated in ~ (ASTM D 1003). The measurements are generally carried out on a plate with a thickness of 3 mm. The ratios indicated refer to ~;
weight ratios.
Other features of the invention will become apparent in the course of the following descrip-tions of exemplary embodiments which are given for illustration of the invention and are not intended to ~e limiting thereof.
I
..
' :`

:"~
;~i.. :

~ -41- ~332038 EXAMPLES

Example 1 Compatible polymer mixtures PM of poly-p-tert.-butyl styrene (polymer P1) and poly-3,3,5-trimethylcyclohexyl acrylate ~polymer P2). Poly-p-tert-butyl styrene (source: Aldrich, Germany;
~spec/c = 16 ml/g) is dissolved in toluene at 20~
by weight. In the same way, a 20% solution of i,, poly-3,3,5-trimethylcyclohexyl acrylate (~spec/c = `
6.9 ml/g) in toluene is produced. The solutions are mixed in the volume ratios of 20/80, 50/50, 00/20. Films are poured of these solutions, dri~d in a vacuum and subsequently evaluated visually.
All mixtures result in clear, colorless films.
15All three films demonstrate no de-mixing when heated to decomposition (> 250C).
` .
Example 2 ;`-Poly-p-tert.-butyl styren~ according to Example 1 is mixed with poly-3,3,5-trimethyl-cyclohexyl methacrylate (polymer P2 (~spec/c = 6-3 ml/g) as described in Example 1.
At every mixture ratio (20/80, 50/50, 80/20) compatible polymer films, clear as glass, result; ~ ;
they demonstrate no de-mixing when heated to temperatures of approximately 350C.

':

., :.' ".
, .;

Example 3 Poly-p-tert.-butyl styrene according to Example 1 is mixed with polycyclohexyl methaCrylate (~spec/c = 38 ml/g) as described in Example 1, as a 20% solution in toluene, and a polymer film is produced.
Mixture ratio: 50% by weight poly-p-tert.-butyl styrene 50% by weight polycyclohexyl methacrylate A polymer film, clear as glass, is obtained; it hecomes cloudy when heated to 160C (de-mixing).

Example 4 The process is the same as in Example 3, but ;
15 polycyclohexyl acrylate is selected as polymer P2. ;
A polymer film, clear as glass, results; it becomes cloudy when heated to 80C. Polymer mixtures according to Example 3 and Example 4 are therefore very well suited for use as an optical data storage plate according to DE-A 34 36 476.5.

Example 5 ~; Production of a plastic plate with tempera- ;~
ture-controlled transparency. 20 parts poly-p-; tert.-butyl styrene according to Example 1 are ~ 25 dissolved in 80 ~' ; ' :

' :;, . ., ~
: ~ ' . ` ,'' ' ~ .~, - ~43~ 1332038 parts cyclohexyl acrylate. 0.1 part tert. butyl perneodecanoate is added as an initiator and 0.5 parts `
dodecyl mercaptan is added as a regulator. The polymer solution is polymerized to form a clear, colorless plate with a thickness of 3 mm between t-~o glass plates. When heated to approximately 80C, this plate `
becomes snow-white. -~
:, .
Examole 6 - Com~arative ExamDl~
The process is the same as in Example 5, but the poly-p-tert.-butyl styrene is dissolved in 80 parts MMA
and the polymerization is carried out. A non- ~
homogeneous, non-compatible, non-transparent plastic ~;`
plate results.

ExamDle 7 - Com~arative Exam~le ;
The process is the same as in Example 5, but the poly-p-tert-butyl styrene is dissolved in 80 parts t-butyl methacrylate. Here again, after polymerization, a non-transparent, non-compatible polymer mixture results.

Exam~le 8 - Polymer P2 as a Co~olymer The process is the same as in Example 5, but the ;
poly-p-tert-butyl styrene (20 parts) is dissolved in a mixture of 40 parts propyl methacrylate and 40 parts , ,~.
`

. ` 133%038 cyclohexyl methacrylate. After completion of polymerization, a homogeneous plate, clear as glass, is obtained.

Example 9 The process is the same as in Example 5, but the 20 parts poly-p-tert.-butyl styrene are dissolved in 80 parts 2-ethylhexyl methacrylate.
After the end of polymerization, a compatible plastic plate, clear as glass is obtained.

Example 10 Poly-p-tert.-butyl styrene according to Example 1 is dissolved in toluene at 20% by weight. In the same way, poly-2-ethylhexyl acrylate is dissolved in toluene at 20~ by weight. ~-The solutions are mixed in a ratio of 20/80, 50/50, 80/20. Films are poured from the mixtures.
The films are dried in a vacuum and subsequently evaluated visually. In each case, clear, colorless films result. ~;~

Example 11 Poly-p-methyl styrene (~spec/c = 4 ml/g) is dissolved in toluene at 20% by weight. In the same way, polycyclohexyl methacrylate (~spec/c =
29 ml/g) is dissolved in toluene at 20% by weight.
The solutions ' "'-~

`~','"~',.
~ ~.

X~ ',:' -45- ~332038 are mixed in a ratio of 5/95, 20/80, 50/50, 80/20, 95/5. Films are poured from the mixtures and dried. All the mixtures yield clear, colorless films.
All the films demonstrate no de-mixing when heated up to 250C.

Example 12 20 parts poly-p-methyl styrene (~spec/c = 83 ml/g) are dissolved in 80 parts cyclohexyl acrylate. After adding 0.1 part tert. butyl perneodecanoate and 0.5 parts dodecy] mercaptan, polymerization is carried out for 48 hours at approximately 50C. The polymerization is carried out between glass plates. A colorless plastic plate, clear as glass, with a thickness of 3 mm is ;
obtained (haze < 3%), which also remains clear when heated to > 200C. --Example 13 20 parts poly-p-methyl styrene (~spec/c = 83 ml/g) are dissolved in 60 parts cyclohexyl acrylate and 20 parts 3,3,5-trimethylcyclohexyl acrylate and polymerized according to Example 12 after adding 0.1 part tert. butyl perneodecanoate and 0.5 parts dodecyl mercaptan. A compatible plastic plate, clear as class, is obtained.
X

~_ -46- 1332038 Ex~ 4 -_Copolymer Example 20 parts poly-p-methyl styrene (~spec/c = 83 ml/g) are dissolved in 60 parts cyclohexyl acrylate and 20 parts butyl acrylate, and polymerized according to Example 12 after adding 0.1 part tert.
butyl perneodecanoate and 0.5 parts dodecyl mercaptan. A compatible plastic plate, clear as glass, is obtained.

Example 15 Comparative example with a relationship of the Van der Waals volumes Vw of ~

and X-CHRsR6 not in accordance with the invention.
20 parts poly-p-methyl styrene (~spec/c = 83 .-~
ml/g) are dissolved in 80 parts decyl methacrylate and polymerized according to Example 12. A demixed, cloudy plastic plate results.
Calculation of the Van der Waals volumes: ~

Polymer P1: ~ CN3 : 56.99 cm3/mol ~;

Polymer P2: -1IC-o-(cH2)g-cH3 :120.94 cm3/mol ~
O ' ''~'~

' ~'~,., ,,,~."',.

' ~''' , ,. ,. .:

~ 7_ Therefore, according to relation (1), VW -COO(CH2)9 CH3 X 0.6 = 72.5 cm3/mol, greater than VW
~ CH3 (VW X 56.99 cm3/mol and therefore not in accordance with the invention.
.

Example 16 Comparative example With several characteristics not in accordance with the inven-tion:
1) Disadvantages ratio of the Van der Waals volumes 2) Polymer P1 with only slightly distinct aliphatic part without quarternary carbon;
polymer P2 with large compact hydrocarbon group with one quarternary carbon.
20 parts poly-p-methyl styrene (~Spec/c = 83 ml/g) are dissolved in 80 parts 3,3,5-trimethylcyclo-hexyl methacrylate and polymerized 20according to Example 12. A de-mixed, cloudy ~ ;
plastic plate results. ~-~
Van der Waals volumes:

Polymer P1: ~ CH3 : 56.99 cm3/mol Polymer P2: -ICl-O ~ > : 103.00 cm3/mol O ~

'~;

- ~ -48- 1332038 VW -COO ~ X 0.6 = 61.8 and therefore greater than Vw ~ CH3.

According to (1), this mixture is not in accordance with the invention.

Example 17 From 20 parts poly-p-tert. butyl styrene according to Example 1 and 80 parts isobornyl ~-methacrylate, a solution is produced in toluene, and dried to form a film as in Example 1. A
colorless film, clear as glass, results.

Example 18 ~-20 parts poly-p-tert. butyl styrene according to Example 1 are dissolved in 80 parts benzyl acrylate and polymerized according to Example 12.
A colorless plate, clear as glass, results.
: , -- ,:
: ...... -Example 19 20 parts poly-p-tert. butyl styrene according , to Example 1 are dissolved in 80 parts 2 phenyl ~`
ethyl acrylate and polymerized according to 20 Example 12. A colorless plate, clear as glass, ~`
results.

Example 20 ~;~
A sheet of poly-p-methylstyrene (J = 83 ml/g) 3 mm thick is coated with a 20% b.w. solution of a 25 polymer P2 dissolved in a solvent mixture - ~-consisting of `~`;

. , ' ~ ,':

,_ -49-.

40% b.w. of diacetone alcohol 40% b.w. of isopropanol 20% b.w. of methyl ethylketone.
The coated sheet is dried at 90~C.
The polymer P2 is characterized as follows:
Copolymer, produced by radical polymerization of 49% b.w. of methyl methacrylate, 2% b.w. of cyclohexylacrylate (J = 32 ml/g).
The result is a perfectly clear sheet with a well adhering surface coatlng.

Example 21 . .
The surface of 1 mm sheet of poly-p- ;~
methylstryene (J = 83 ml/g) is covered with lO~m coating of polycyclohexylmethacrylate.
J = 31 ml/g). The sheet thus obtained is ground -and subsequently granulated and the granulate is again extruded to form a 1 mm sheet. In this way the working up of waste material is simulated.
The sheets obtained in this fashion are perfectly clear and not inferior to the original poly-p-methylstyrene sheet.
.

.
. ~.

Claims (12)

1. A molded object comprising a first molded polymer P1 coated with a second polymer P2, wherein polymer P1 comprises at least 30% by weight of monomers having Formula I:

(I) wherein R1 is hydrogen or methyl, R2 is a hydrocarbon group containing 1-18 carbon atoms, wherein said polymer P1 contains less than 20 weight% styrene or .alpha.-methyl styrene, and wherein polymer P2 comprises at least 30% by weight of monomers having Formula II:

(II) wherein R3 is hydrogen, methyl or a group -CH2-X-CHR5R6, X is -C(O)-Z-, -Z-C(O)-, -Z-C(O)-Z'-, wherein Z is oxygen or -NR4, Z' is oxygen or NR4, and R4 is hydrogen or an alkyl group with 1-12 carbon atoms, and -CHR5R6 is an aliphatic or araliphatic hydrocarbon group with 5-24 carbon atoms.

2. The object of claim 1, wherein R5 and R6 are combined in a ring comprising 5-12 carbon atoms.

3. The object of claim 1, wherein R5 is hydrogen or a C1-5 hydrocarbon group and R6 is an aliphatic, araliphatic or aromatic hydrocarbon group with 4-18 carbon atoms.

4. The object of claim 1, wherein the group -X- is -C(O)-O-, -O-C(O)- or -O-C(O)-O-.

5. The object of claim 1, wherein R2 is hydrogen or R3 is hydrogen or methyl.

6. The object of claim 1, wherein R5 and R6 are combined in a cyclohexane ring.

7. The object of claim 1, wherein R6 is a branched aliphatic group with 4-18 carbon atoms.

8. The object of claim 1, wherein R2 is -CCH3R7R8, where R7 is hydrogen or an alkyl group with 1-18 carbon atoms.

9. The object of claim 1, wherein R1 is hydrogen.

10. The object of claim 1, wherein polymer P1 is poly-p-methylstryene and polymer P2 is polycyclohexyl(methyl)acrylate.

11. The object of claim 1, wherein said molded object is a film, plate, sheet, fiber or cable.

12. The object of claim 1, wherein said molded object is produced by injection, pressing, extrusion, rolling or casting.