United States Patent [19]
`United States Patent [191
`Taubitz et al.
`Taubitz et al.
`
`[11] Patent Number:
`[11] Patent Number:
`[45] Date of Patent:
`[45] Date of Patent:
`
`4,965,318
`4,965,318
`Oct. 23, 1990
`Oct. 23, 1990
`
`[54] THERMOPLASTIC MOLDING MATERIALS
`[54] THERMOPLASTIC MOLDING MATERIALS
`BASED ON NYLONS AND STYRENE
`BASED ON NYLONS AND STYRENE
`COPOLYMERS
`COPOLYMERS
`Inventors: Christof Taubitz, Wachenheim;
`[75]
`[75] Inventors: Christof Taubitz, Wachenheim;
`Erhard Seiler, Ludwigshafen;
`Erhard Seiler, Ludwigshafen;
`Juergen Hambrecht,
`Juergen Hambrecht,
`Miinster-Hiltrup; Konrad Mitulla,
`Miinster-Hiltrup; Konrad Mitulla,
`Ludwigshafen; Horst Reimann,
`Ludwigshafen; Horst Reimann,
`Worms, all of Fed. Rep. of Germany
`Worms, all of Fed. Rep. of Germany
`[73] Assignee: BASF Aktiengesellschaft,
`[73] Assignee: BASF Aktiengesellschaft,
`Ludwigshafen, Fed. Rep. of
`Ludwigshafen, Fed. Rep. of
`Germany
`Germany
`[21] Appl. No.: 218,977
`[21] Appl. No.: 218,977
`[22] Filed:
`Jul. 14, 1988
`[22] Filed:
`Jul. 14, 1988
`
`Related US. Application Data
`Related U.S. Application Data
`[62] Division of Ser. No. 10,437, Feb. 3, 1987, abandoned.
`Division of Ser. No. 10,437, Feb. 3, 1987, abandoned.
`[62]
`[30]
`Foreign Application Priority Data
`[30]
`Foreign Application Priority Data
`Feb. 12, 1986 [DE] Fed. Rep. of Germany ....... 3604349
`Feb. 12, 1986 [DE] Fed, Rep. of Germany ..... .. 3604349
`[51]
`Int. Cl.s .............................................. C08L 77/00
`[51] Int. Cl.5 ............................................ .. C08L 77/00
`[52] U.S. Cl ..................................... 525/179; 525/182;
`[52] US. Cl. . . . . . .
`. . . .. 525/179; 525/182;
`525/183
`525/183
`[58] Field of Search ........................ 525/182, 179, 183
`[58] Field of Search ...................... .. 525/182, 179, 183
`[56]
`References Cited
`[56]
`References Cited
`U.S. PATENT DOCUMENTS
`U.S. PATENT DOCUMENTS
`3,334,153 8/1967 Fukushima et aI ................. 525/179
`3,334,153 8/1967 Fukushima et al. .............. ” 525/179
`4,590,242 5/1986 Hom et al. .......................... 525/183
`4,598,125 7/1986 Hom et aI ........................... 525/183
`4,598,125 7/1986 Horn et al. . . . .
`. . . . .. 525/183
`4,612,346 9/1986 Chiba et aI .......................... 525/182
`4,612,346 9/1986 Chiba et a1. ....................... .. 525/ 182
`Primary Examiner-Ana L. Carrillo
`Primary Examiner——Ana L. Carrillo
`Attorney, Agent, or Firm-ObIon, Spivak, McClelland,
`Attorney, Agent, or Firm—Oblon, Spivak, McClelland,
`Maier & Neustadt
`Maier & Neustadt
`ABSTRACT
`[57]
`[57]
`ABSTRACT
`Thermoplastic molding materials contain
`Thermoplastic molding materials contain
`(A) from 5 to 95% by weight of a nylon and
`(A) from 5 to 95% by weight of a nylon and
`(B) from 5 to 95% by weight of a copolymer composed
`(B) from 5 to 95% by weight of a copolymer composed
`of
`of
`
`4,590,242 5/1986 Horn et al. . . . . . . . .
`
`. . . . .. 525/183
`
`(B1) from 50 to 99.9% by weight of a styrene of the
`(BI) from 50 to 99.9% by weight of a styrene of the
`general formula I
`general formula I
`
`(I)
`
`where R I is alkyl or 1 to 4 carbon atoms or hydrogen,
`where R1 is alkyl or 1 to 4 carbon atoms or hydrogen,
`R 2 is alkyl of 1 to 6 carbon atoms or halogen and m is
`R2 is alkyl of 1 to 6 carbon atoms or halogen and m is
`0, 1,2 or 3,
`0, 1, 2 or 3,
`(B2) from 0.1 to 30% by weight of a monomer contain(cid:173)
`(B2) from 0.1 to 30% by weight of a monomer contain
`ing epoxide groups (II)
`ing epoxide groups (II)
`
`_
`
`I
`I
`l
`I
`-c--c-
`'-/ o
`\ /
`O
`or of a m,?nomer containing lactam groups (III)
`or of a monomer containing lactam groups (III)
`
`cg
`
`_N
`\
`R3
`/
`O=C
`
`(II)
`(II)
`
`(III)
`(11!)
`
`or of a monomer containing halobenzyl groups (IV)
`or of a monomer containing halobenzyl groups (IV)
`
`(cH2x),,
`
`(IV)
`(IV)
`
`(114)’
`
`where R3 is a divalent, branched or straight-chain·
`where R3 is a divalent, branched or straight-chain.
`alkyl group of2 to 15 carbon atoms, R4 is alkyl of not
`alkyl group of 2 to 15 carbon atoms, R4 is alkyl of not
`more than 6 carbon atoms, X is halogen, n is 1,2 or 3
`more than 6 carbon atoms, X is halogen, n is 1, 2 or 3
`.
`and r is 0, 1, 2 or 3, and
`andrisO, 1,2or3, and
`1'
`(B3) from 0 to 48% by weight of further comonomers.
`(B3) from 0 to 48% by weight of further comonomers.
`
`4 Claims, No Drawings
`4 Claims, No Drawings
`
`Page 1 of 7
`
`PETITIONERS' EXHIBIT 1019
`
`

`

`1
`1
`
`THERMOPLASTIC MOLDING MATERIALS
`THERMOPLASTIC MOLDING MATERIALS
`BASED ON NYLONS AND STYRENE
`BASED ON NYLONS AND STYRENE
`COPOLYMERS
`COPOLYMERS
`
`This application is a division of U.S. application Ser.
`This application is a division of U.S. application Ser.
`No. 07/010,437, ftled Feb. 3, 1987, and now abandoned.
`No. 07/010,437, ?led Feb. 3, 1987, and now abandoned.
`The present invention relates to novel thermoplastic
`The present invention relates to novel thermoplastic
`molding materials containing
`molding materials containing
`(A) from 5 to 95% by weight of a nylon and
`(A) from 5 to 95% by weight of a nylon and
`(B) from 5 to 95% by weight of a copolymer com(cid:173)
`(B) from 5 to 95% by weight of a copolymer com
`posed of
`posed of
`(BI) from 50 to 99.9% by weight of a styrene of the
`(B1) from 50 to 99.9% by weight of a styrene of the
`general formula I
`general formula I
`
`(112),”
`
`(I)
`
`20
`20
`
`where R 1 is alkyl of 1 to 4 carbon atoms or hydrogen,
`where R1 is alkyl of 1 to 4 carbon atoms or hydrogen,
`R 2 is alkyl of 1 to 6 carbon atoms or halogen and m is 0,
`R2 is alkyl of 1 to 6 carbon atoms or halogen and m is 0,
`I, 2 or 3,
`1, 2 or 3,
`25
`(B2) from 0.1 to 30% by weight of a monomer con- 25
`(B2) from 0.1 to 30% by weight of a monomer con
`taining epoxide groups (II)
`taining epoxide groups (II)
`
`4,965,318
`4,965,318
`2
`2
`this manner have poorly reproducible properties, i.e.
`this manner have poorly reproducible properties, i.e.
`constant product quality is not ensured.
`constant product quality is not ensured.
`DE-A 30 37 520 describes block copolymers contain
`DE-A 30 37 520 describes block copolymers contain(cid:173)
`ing blocks of styrene copolymers and nylons. These
`ing blocks of styrene copolymers and nylons. These
`materials have a very high melt flow index, which is a
`5 materials have a very high melt flow index, which is a
`disadvantage for processing.
`disadvantage for processing.
`EP-A 80 720 attempts to avoid this problem by using
`EP-A 80 720 attempts to avoid this problem by using
`styrene polymers containing carboxamide groups.
`styrene polymers containing carboxamide groups.
`However, products produced from these materials have
`10 However, products produced from these materials have
`a pronounced tendency to yellow.
`a pronounced tendency to yellow.
`It is an object of the present invention to provide
`It is an object of the present invention to provide
`molding materials consisting of nylons and styrene pol
`molding materials consisting of nylons and styrene pol(cid:173)
`ymers, the said materials possessing good mechanical
`ymers, the said materials possessing good mechanical
`properties and being capable of being processed to high
`15 properties and being capable of being processed to high
`15
`quality moldings.
`quality moldings.
`We have found that this object is achieved, according
`We have found that this object is achieved, according
`to the invention, by thermoplastic molding materials
`to the invention, by thermoplastic molding materials
`containing
`containing
`(A) from 5 to 95% by weight of a nylon and
`(A) from 5 to 95% by weight of a nylon and
`(B) from 5 to 95% by weight of a copolymer com
`(B) from 5 to 95% by weight of a copolymer com(cid:173)
`posed'of
`posed·of
`(B1) from 50 to 99.9% by weight of a styrene of the
`(BI) from 50 to 99.9% by weight of a styrene of the
`general formula I
`general formula I
`
`(I)
`
`(II)
`(II)
`
`(III)
`(III)
`
`_
`
`I
`I
`I
`I
`-c--c-
`'-./
`\ /
`o
`0
`
`C
`
`or of a monomer containing lactam groups (III)
`or of a monomer containing lactam groups (III)
`
`_.N
`\
`R3
`
`0=c
`
`(II)
`(II)
`
`30
`30
`
`(112)»;
`
`where R1 is alkyl of 1 to 4 carbon atoms or hydrogen,
`where R I is alkyl of I to 4 carbon atoms or hydrogen,
`R2 is alkyl of 1 to 6 carbon atoms or halogen and m is 0,
`R2 is alkyl of I to 6 carbon atoms or halogen and m is 0,
`35
`35 1,2 or 3,
`1, 2 or 3,
`(B2) from 0.1 to 30% by weight of a monomer con(cid:173)
`(B2) from 0.1 to 30% by weight of a monomer con
`taining epoxide groups (II)
`taining epoxide groups (II)
`
`(III)
`(III)
`
`or of a monomer containing halobenzyl groups (IV)
`or of a monomer containing halobenzyl groups (IV)
`
`40
`
`(IV)
`
`I
`I
`-c--c(cid:173)
`'-./
`o
`
`45 or of a monomer containing lactam groups (III)
`or of a monomer containing lactam groups (III)
`45
`
`_N
`
`=C
`
`where R3 is a divalent, branched or straight-chain alkyl(cid:173)
`where R3 is a divalent, branched or straight-chain alkyl
`50
`ene group of 2 to 15 carbon atoms, R4 is alkyl of not 50
`ene group of 2 to 15 carbon atoms, R4 is alkyl of not
`more than 6 carbon atoms, X is halogen, n is 1, 2 or 3
`more than 6 carbon atoms, X is halogen, n is 1, 2 or 3
`and r is 0, I, 2 or 3, and
`and r is 0,1, 2 or 3, and
`(B3) from 0 to 48% by weight of further comono(cid:173)
`(B3) from 0 to 48% by weight of further comono
`mers.
`mers.
`The present invention furthermore relates to the use 55
`55
`The present invention furthermore relates to the use
`of such molding materials for the production of mold(cid:173)
`of such molding materials for the production of mold
`ings, and to moldings produced from the molding mate(cid:173)
`ings, and to moldings produced from the molding mate
`rials.
`rials.
`U.S. Pat. No. 3,134,746 describes blends of polycap(cid:173)
`US Pat. No. 3,134,746 describes blends of polycap
`rolactam and acrylonitrile/butadiene/ styrene copoly
`rolactam and acrylonitrile!butadiene/styrene copoly- 60
`mers (ABS).
`mers (ABS).
`Because of the incompatibility of the two polymers
`Because of the incompatibility of the two polymers
`forming the blend, the moldings produced from these
`forming the blend, the moldings produced from these
`blends have poor mechanical properties; the moldings
`blends have poor mechanical properties; the moldings
`separate into layers (delamination).
`65
`separate into layers (delamination).
`65
`According to U.S. Pat. No. 3,485,777, peroxides are
`According to US. Pat. No. 3,485,777, peroxides are
`used in order to increase the compatibility of nylons and
`used in order to increase the compatibility of nylons and
`styrene polymers. However, the products produced in
`styrene polymers. However, the products produced in
`
`or of a monomer containing halobenzyl groups (IV)
`or of a monomer containing halobenzyl groups (IV)
`
`(Cl-12X)"
`
`(IV)
`(IV)
`
`where R3 is a divalent, branched or straight-chain alkyl
`where R3 is a divalent, branched or straight-chain alkyl
`group of 2 to 15 carbon atoms, R4 is alkyl of not more
`group of 2 to 15 carbon atoms, R4 is alkyl of not more
`than carbon atoms, X is halogen, n is l, 2 or 3 and r is 0,
`than carbon atoms, X is halogen, n is 1,2 or 3 and r is 0,
`1,2 or 3, and
`l, 2 or 3, and
`(B3) from O to 48% by weight of further comono
`(B3) from 0 to 48% by weight of further comono(cid:173)
`mers.
`mers.
`Preferred molding materials of this type are described
`Preferred molding materials of this type are described
`in the subclaims.
`in the subclaims.
`
`Page 2 of 7
`
`

`

`I
`I
`-c--c-
`'\../
`o
`
`(11)
`(II)
`
`4,965,318
`4,965,318
`4
`4
`3
`3
`The copolymers B contain component B2 as compo- '
`The novel thermoplastic molding materials are distin(cid:173)
`The novel thermoplastic molding materials are distin
`The copolymers B contain component B; as compo- ‘
`_ guished by good mechanical properties, in particular
`nents which are essential to the invention. The compati(cid:173)
`guished by good mechanical properties, in particular
`nents which are essential to the invention. The compati
`high impact strength (including multiaxial impact
`bility-improving action of this component is probably
`high impact strength (including multiaxial impact
`bility-improving action of this component is probably
`strength) and good resistance to solvents. The resis
`strength) and good resistance to solvents. The resis(cid:173)
`attributable to an interaction of the functional group of
`attributable to an interaction of the functional group of
`tance to chemicals, heat and abrasion is substantially 5
`tance to chemicals, heat and abrasion is substantially
`component B; with the components B1 and A. Whether
`component B2 with the components Bl and A. Whether
`better than that of styrene polymers, and the molding
`better than that of styrene polymers, and the molding
`this is a physical interaction or involves the formation of
`this is a physical interaction or involves the formation of
`materials according to the invention exhibit substan
`materials according to the invention exhibit substan(cid:173)
`covalent bonds cannot be stated with certainty.
`covalent bonds cannot be stated with certainty.
`tially less shrinkage than nylons. The good processabil
`tially less shrinkage than nylons. The good processabil(cid:173)
`Component B2 is a monomer possessing epoxide(II)
`Component B2 is a monomer possessing epoxide(lI)
`ity and flow are also particularly advantageous.
`ity and flow are also particularly advantageous.
`or lactam(I1I) or halobenzyl groups (IV).
`or lactam(III) or halobenzyl groups (IV).
`The novel molding materials contain, as component 10
`The novel molding materials contain, as component
`Among the monomers which contain epoxide groups
`Among the monomers which contain epoxide groups
`A, a nylon in an amount off rom 5 to 95, preferably from
`A, a nylon in an amount of from 5 to 95, preferably from
`(11)
`(II)
`10 to 90, particularly preferably from 35 to 80, % by
`10 to 90, particularly preferably from 35 to 80, % by
`weight.
`weight.
`There are no particular restrictions with regard to the
`There are no particular restrictions with regard to the
`structure and molecular weight of the nylons, but ny
`structure and molecular weight of the nylons, but ny- 15
`Ions having a molecular weight of from 8,000 to 60,000
`lons having a molecular weight of from 8,000 to 60,000
`are generally preferred.
`are generally preferred.
`Examples of preferred nylons are those which are
`Examples of preferred nylons are those which are
`derived from lactams having from 7 to 13 ring members,
`derived from lactams having from 7 to 13 ring members,
`20
`such as polycaprolactam, polycapryllactam or polylau- 20
`such as Polycaprolactam, polycapryllactam or polylau
`ryllactam, and nylons which are obtained by reacting a
`ryllactam, and nylons which are obtained by reacting a
`dicarboxylic acid with a diamine. Alkanedicarboxylic
`dicarboxylic acid with a diamine. Alkanedicarboxylic
`acids of 6 to 12, in particular 6 to 10, carbon atoms,
`acids of 6 to 12, in particular 6 to 10, carbon atoms,
`terephthalic acid and isophthalic acid are among the
`terephthalic acid and isophthalic acid are among the
`25
`preferred dicarboxylic acids, while alkanediamines of 6
`preferred dicarboxylic acids, while alkanediamines of 6 25
`to 12, in particular 6 to 8, carbon atoms, p-xylylenedia(cid:173)
`to 12, in particular 6 to 8, carbon atoms, p-xylylenedia
`mine,
`di-(4-aminophenyl)-methane,
`di-(4-aminocy
`mine,
`di-( 4-aminophenyl)-methane,
`di-( 4-aminocy(cid:173)
`clohexyl)-methane and 2,2-di-(4-aminophenyl)-propane
`clohexyl)-methane and 2,2-di-( 4-aminophenyl)-propane
`are among the preferred diamines. Both the dicarbox(cid:173)
`are among the preferred diamines. Both the dicarbox
`ylic acids and the diamines can be used individually or 30
`ylic acids and the diamines can be used individually or
`in any combination. It is also possible, and frequently
`in any combination. It is also possible, and frequently
`advantageous, to use blends of a plurality of the stated
`advantageous, to use blends of a plurality of the stated
`nylons for the thermoplastic molding materials.
`nylons for the thermoplastic molding materials.
`Polycaprolactam, polyhexamethylene adipamide and
`Polycaprolactam, polyhexamethylene adipamide and
`35
`nylons composed of hexamethylenediamine and iso
`nylons composed of hexamethylenediamine and iso- 35
`phthalic acid andlor terephthalic acid have become
`phthalic acid and/or terephthalic acid have become
`particularly important industrially.
`particularly important industrially.
`The nylons which can be used according to the in(cid:173)
`The nylons which can be used according to the in
`vention are known per se or can be prepared from the
`- vention are known per se or can be prepared from the
`monomers by a conventional process, so that further 40
`monomers by a conventional process, so that further
`information is super?uous here.
`information is superfluous here.
`The novel molding materials contain, as component
`The novel molding materials contain, as component
`B, copolymers composed of styrene andlor substituted
`B, copolymers composed of styrene and/or substituted
`styrenes B1 and monomers B2 containing epoxide
`styrenes Bl and monomers B2 containing epoxide
`groups (II) or lactam groups (III) or halobenzyl groups 45
`groups (II) or lactam groups (III) or halobenzyl groups
`(IV), and, if required, further copolymerizable mono(cid:173)
`(IV), and, if required, further copolymerizable mono
`mers B3.
`mers B3.
`The amount of styrene Bl in component B is from 50
`The amount of styrene B1 in component B is from 50
`to 99.9, preferably from 70 to 95, % by weight. The
`to 99.9, preferably from 70 to 95, % by weight. The
`50
`styrenes are of the general formula I
`50
`styrenes are of the general formula I
`
`those possessing a plurality of epoxide groups are pre(cid:173)
`those possessing a plurality of epoxide groups are pre
`ferred. In principle, all epoxide-containing monomers
`ferred. In principle, all epoxide-containing monomers
`are suitable if it is ensured that the epoxide group is
`are suitable if it is ensured that the epoxide group is
`present in the free form after the reaction.
`present in the free form after the reaction.
`It may be stated here that the free epoxide groups
`It may be stated here that the free epoxide groups
`may also be introduced into polymer B by epoxidation
`may also be introduced into polymer B by epoxidation
`of polymers of the monomers B1 with epoxidizing
`of polymers of the monomers Bl with epoxidizing
`agents.
`agents.
`The amount of the epoxide-containing monomer is
`The amount of the epoxide-containing monomer is
`from 0.1 to 30, preferably from 0.5 to 20, particularly
`from 0.1 to 30, preferably from 0.5 to 20, particularly
`preferably from 1 to 10, % by weight, based on compo
`preferably from 1 to 10, % by weight, based on compo(cid:173)
`nent B.
`nent B.
`Glycidyl-containing monomers, e.g. vinyl glycidyl
`Glycidyl-containing monomers, e. g. vinyl glycidyl
`ether or allyl glycidyl ether, and (meth)actylates con(cid:173)
`ether or allyl glycidyl ether, and (meth)acrylates con
`taining glycidyl groups, in particular glycidyl acrylate
`taining glycidyl groups, in particular glycidyl acrylate
`and glycidyl methacrylate, may be mentioned here
`and glycidyl methacrylate, may be mentioned here
`merely by way of typical examples of epoxide-contain
`merely by way of typical examples of epoxide-contain(cid:173)
`ing monomers B2.
`ing monomers B2.
`Typical examples of preferred components B contain
`Typical examples of preferred components B contain(cid:173)
`ing epoxide groups are copolymers of
`ing epoxide groups are copolymers of
`(B1) from 90 to 99% by weight of styrene, a-methyls
`(Bl) from 90 to 99% by weight of styrene, a-methyls(cid:173)
`tyrene andlor p-methylstyrene and
`tyrene and/or p-methylstyrene and
`(B2) from 1 to 10% by weight of glycidyl (meth)acry
`(B2) from 1 to 10% by weight of glycidyl (meth)acry(cid:173)
`late or
`late or
`(B1) from 50 to 91% by weight of styrene, a-methyls
`(Bl) from 50 to 91 % by weight of styrene, a-methyls(cid:173)
`tyrene andlor p-methylstyrene,
`tyrene and/or p-methylstyrene,
`~
`(B2) from 1 to 10% by weight of glycidyl (meth)acry(cid:173)
`. (B2) from 1 to 10% by weight of glycidyl (meth)acry
`late and
`late and
`(B3) from 8 to 40% by weight of acrylonitrile andlor
`(B3) from 8 to 40% by weight of acrylonitrile and/ or
`methacrylonitrile.
`methacrylonitrile.
`Monomers containing lactam groups (III) are useful
`Monomers containing lactam groups (III) are useful
`as the second group of monomers B2.
`as the second- group of monomers B2.
`These monomers contain a lactam group of the gen(cid:173)
`These monomers contain a lactam group of the gen
`eral formula III
`eral formula III
`
`o
`‘ /
`~
`-N--'-C
`C
`/
`'\..
`\ /
`R3
`R3
`
`(III)
`(III)
`
`(112)»
`
`(I)
`
`55
`55
`
`where R 1 is alkyl of 1 to 4 carbon atoms, preferably
`where R1 is alkyl of 1 to 4 carbon atoms, preferably
`methyl, or hydrogen, R2 is halogen, preferably chlorine,
`methyl, or hydrogen, R 2 is halogen, preferably chlorine, 60
`60
`or alkyl of 1 to 6 carbon atoms, preferably methyl or
`or alkyl of 1 to 6 carbon atoms, preferably methyl or
`ethyl, and m is 0, 1, 2 or 3. Examples of these are a(cid:173)
`ethyl, and m is 0, l, 2 or 3. Examples of these are a
`methylstyrene, 0-, m- and p-methylstyrene, m-ethylsty(cid:173)
`methylstyrene, 0-, m- and p-methylstyrene, m-ethylsty
`rene, dimethylstyrene, chlorostyrene and mixtures of
`rene, dimethylstyrene, chlorostyrene and mixtures of
`these compounds.
`these compounds.
`65
`65
`Of course, it is also possible to use mixtures of various
`Of course, it is also possible to use mixtures of various
`substituted styrenes or mixtures of styrene and substi(cid:173)
`substituted styrenes or mixtures of styrene and substi
`tuted styrenes, which 'frequently even has advantages.
`tuted styrenes, which frequently even has advantages.
`
`where R 3 is a branched or straight-chain alkylene group
`where R3 is a branched or straight-chain alkylene group
`of 2 to 15 carbon atoms.
`of 2 to 15 carbon atoms.
`Among these monomers, preferred compounds are
`Among these monomers, preferred compounds are
`those which can be polymerized or copolymerized to
`those which can be polymerized or copolymerized to
`nylons according to Houben-Weyl, Methoden der or(cid:173)
`nylons according to Houben-Weyl, Methoden der or
`ganischen Chemie, Vol. X/2, pages 511-87 (1975) and
`ganischen Chemie, Vol. X/2, pages 511-87 (1975) and
`Vol. XIV 12, pages 111-131.
`Vol. XIV/2, pages 111-131.
`/3-Propiolactams (azetidin-2-ones) of the general for(cid:173)
`B-Propiolactams (azetidin-Z-ones) of the general for
`mula (V)
`mula (V)
`
`Page 3 of 7
`
`

`

`5
`
`(V)
`
`4,965,318
`4,965,318
`6
`6
`(B2) from 0.1 to 5% by weight of N-(meth)acryloyl-e
`(B2) from 0.1 to 5% by weight of N-(meth)acryloyl-E(cid:173)
`caprolactam or, where monomers B3 are present,
`caprolactam or, where monomers B3 are present,
`(B1) from 55 to 91% by weight of styrene, a-methylsty
`(Bl) from 55 to 91 % by weight of styrene, a-methylsty(cid:173)
`rene and/or p-methylstyrene,
`rene and/or p-methylstyrene,
`(B2) from 0.1 to 5% by weight of N-(meth)acryloyl-e
`5 (B2) from 0.1 to 5% by weight of N-(meth)acryloyl-E(cid:173)
`caprolactam and
`caprolactam and
`(B3) from 8 to 40% by weight of (meth)acrylonitrile.
`(B3) from 8 to 40% by weight of (meth)acrylonitrile.
`Monomers which contain halobenzyljgroups (IV)
`Monomers which contain halobenzylgroups (IV)
`
`10
`
`(CI-12X)”
`
`(IV)
`(IV)
`
`where R5 to R8 are each alkyl of 1 to 6 carbon atoms or
`where R5 to R8 are each alkyl of l to 6 carbon atoms or
`hydrogen, may be mentioned here merely as typical
`hydrogen, may be mentioned here merely as typical
`examples. These compounds are described by R. Graf
`examples. These compounds are described by R. Graf
`in Angew. Chem. 74 (1962), 523-530 and by H. Bastian
`in Angew. Chem. 74 (1962), 523-530 and by H. Bastian
`15
`in Angew. Chem. 80 (1968), 304-312. Examples of these 15
`in Angew. Chem. 80 (1968), 304-312. Examples of these
`are 3,3' -dimethyl-3-propiolactam, 2-pyrrolidones
`are 3,3’-dimethyl-3-propiolactam, 2-pyrrolidones
`
`\
`(CH2);
`/
`c
`/
`o
`
`e-caprolactam
`e-caprolactam
`
`c
`/
`
`O Q
`
`7-enantholactam, 8-capryllactam and 12-laurolactam, as
`7-enantholactam, 8-capryllactam and l2-laurolactam, as
`also described by H. Dachs, Angew. Chem. 74 (1962),
`also described by H. Dachs, Angew. Chem. 74 (1962),
`540-45.
`540-45.
`Among these compounds, 2-pyrrolidones and E(cid:173)
`Among these compounds, 2-pyrrolidones and e
`caprolactams are particularly preferred.
`caprolactams are particularly preferred.
`The lactam groups III are preferably incorporated
`The lactam groups III are preferably incorporated
`into the monomer B2 via a carbonyl group on the nitro- 40
`into the monomer B2 via a carbonyl group on the nitro
`gen, as in moiety (VI)
`gen, as in moiety (VI)
`
`35
`35
`
`II I '\.
`
`-C-N
`o
`
`/(CHz)n
`
`(VI)
`
`(VII)
`
`(VII)
`
`where R4 is alkyl of 1 to 6 carbon atoms, X is halogen,
`where R4 is alkyl of 1 to 6 carbon atoms, X is halogen,
`preferably CI or Br, n is 1, 2 or 3 and r is 0, 1, 2 or 3, may
`preferably C1 or Br, 11 is l, 2 or 3 and r is 0, l, 2 or 3, may
`be mentioned as the third group of suitable monomers
`be mentioned as the third group of suitable monomers
`B2.
`20 B2.
`20
`The halobenzyl groups can be introduced into the
`The halobenzyl groups can be introduced into the
`copolymer B by conversion of‘ a methyl-containing
`copolymer B by conversion of a methyl-containing
`styrene polymer which reacts with halogenating agents
`styrene polymer which reacts with halogenating agents
`or by chloromethylation of an aromatic polymer, but
`or by chloromethylation of an aromatic polymer, but
`the preparation by copolymerization of styrene and/or
`25 the preparation by copolymerization of styrene and/or
`25
`substituted styrenes and halobenzyl-carrying monomers
`substituted styrenes and halobenzyl-carrying monomers
`is preferred. Regarding the adhesion-improving action,
`is preferred. Regarding the adhesion-improving action,
`however, no significant differences are observed be(cid:173)
`however, no signi?cant differences are observed be
`tween the polymers B prepared by different methods.
`tween the polymers B prepared by different methods.
`Among the monomers containing halobenzyl groups
`30 Among the monomers containing halobenzyl groups
`30
`(IV), only m- and p-chloromethylvinylbenzene are
`(IV), only m- and p-chloromethylvinylbenzene are
`mentioned here as typical examples, owing to the fact
`mentioned here as typical examples, owing to the fact
`that they are readily available. The amount of these
`that they are readily available. The amount of these
`compounds in component B is from 0.1 to 30, preferably
`compounds in component B is from 0.1 to 30, preferably
`from 0.1 to 20, in particular from 0.5 to 7.5, % by
`from 0.1 to 20, in particular from 0.5 to 7.5, % by
`weight, so that the following compositions are examples
`weight, so that the following compositions are examples
`of preferred halobenzyl-containing components B:
`of preferred halobenzyl-containing components B:
`(B1) from 92.5 to 99.5% by weight of styrene, a-meth
`(Bl) from 92.5 to 99.5% by weight of styrene, a-meth(cid:173)
`ylstyrene and/or p-methylstyrene
`ylstyrene and/or p-methylstyrene
`(B2) from 0.5 to 7.5% by weight of p- and/or m(cid:173)
`(B2) from 0.5 to 7.5% by weight of p- and/or m
`chloromethylvinylbenzene
`chloromethylvinylbenzene
`and, where further monomers B3 are present,
`and, where further monomers B3 are present,
`(B1) from 50 to 91% by weight of styrene, a-methylsty
`(Bl) from 50 to 91 % by weight of styrene, a-methylsty(cid:173)
`rene and/or p-methylstyrene,
`rene and/or p-methylstyrene,
`45 (B2) from 0.5 to 7.5% by weight of p- and/or m(cid:173)
`(B2) from 0.5 to 7.5% by weight of p- and/or m
`45
`chloromethylvinylbenzene and
`chloromethylvinylbenzene and
`(B3) from 8 to 40% by weight of (meth)acrylonitrile.
`(B3) from 8 to 40% by weight of (meth)acrylonitrile.
`As stated for some abovementioned particularly pre(cid:173)
`As stated for some abovementioned particularly pre
`ferred components B, up to 48% by weight of other
`ferred components B, up to 48% by weight of other
`A particularly preferred example of this is N-(meth
`A particularly preferred example of this is N-(meth- 50 comonomers may also be present in addition to compo-
`comonomers may also be present in addition to compo
`50
`)acryloyl-e-caprolactam (VII)
`)acryloyl-E-caprolactam (VII)
`nents BI and B2. (Meth)acrylonitrile and alkyl (meth)a(cid:173)
`nents B1 and B2. (Meth)acrylonitrile and alkyl (meth)a
`crylates where alkyl is of 1 to 12 carbon atoms may be
`crylates where alkyl is of 1 to 12 carbon atoms may be
`mentioned here merely by way of example, speci?c
`mentioned here merely by way of example, specific
`examples being methyl acrylate, ethyl acrylate, isopro
`examples being methyl acrylate, ethyl acrylate, isopro-
`pyl and n-propyl acrylate, primary, secondary and ter
`55 pyl and n-propyl acrylate, primary, secondary and ter(cid:173)
`55
`tiary butyl acrylate, 2-ethylhexyl acrylate and dodecyl
`tiary butyl acrylate, 2-ethylhexyl acrylate and dodecyl
`acrylate.
`acrylate.
`_
`Component B can be prepared by a conventional
`Component B can be prepared by a conventional
`polymerization method, such as mass polymerization,
`polymerization method, such as mass polymerization,
`suspension polymerization, emulsion polymerization or
`60 suspension polymerization, emulsion polymerization or
`solution polymerization, either continuously or batch
`solution polymerization, either continuously or batch(cid:173)
`wise. Such methods are known per se and are described
`wise. Such methods are known per se and are described
`in the literature, so that no further information is neces-
`in the literature, so that no further information is neces
`sary here.
`sary here.
`The amount of component B in the novel molding
`The amount of component B in the novel molding
`materials is from 5 to 95, preferably from 10 to 90 and
`materials is from 5 to 95, preferably from 10 to 90 and
`particularly preferably from 20 to 65, % by weight,
`particularly preferably from 20 to 65, % by weight,
`based on the total weight of components A and B.
`based on the total weight of components A and B.
`
`C
`c
`/
`~
`o
`o
`
`1'9
`R9
`I
`II I '\.
`CHz=C-C-N
`CH2=C—C—N
`\
`o
`O
`(CH2)s
`/(CHz)s
`/
`C
`C
`/
`~ o
`0
`
`where R9 is hydrogen or methyl.
`where R9 is hydrogen or methyl.
`The amount of monomers B2 possessing lactam
`The amount of monomers B2 possessing lactam
`groups in components B is from 0.1 to 30, preferably
`groups in components B is from 0.1 to 30, preferably
`from 0.1 to 5, % by weight, based on component B.
`from 0.1 to 5, % by weight, based on component B.
`This gives, for example, the following compositions
`This gives, for example, the following compositions 65
`65
`for component B:
`for component B:
`(BI) from 95 to 99.9% by weight of styrene, a-methyls(cid:173)
`(B1) from 95 to 99.9% by weight of styrene, a-methyls
`tyrene and/or p-methylstyrene and
`tyrene and/or p-methylstyrene and
`
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`4,965,318
`4,965,318
`7
`8
`8
`7
`is necessary. Under certain conditions, the components
`is necessary. Under certain conditions, the components
`The polymers B employed preferably have a molecu(cid:173)
`The polymers B employed preferably have a molecu
`forming the molding material may react with one an(cid:173)
`lar weight of from 5,000 to 1,000,000, in particular from
`forming the molding material may react with one an
`lar weight of from 5,000 to 1,000,000, in particular from
`80,000 to 500,000.
`other. The order in which the components are mixed
`other. The order in which the components are mixed
`80,000 to 500,000.
`may be varied, i.e. all of the components may be mixed
`Component B may also be toughened. Such polymers
`Component B may also be toughened. Such polymers
`may be varied, i.e. all of the components may be mixed
`together or two or three components may be mixed
`are familiar to the skilled worker in the form of high 5
`together or two or three components may be mixed
`are familiar to the skilled worker in the form of high
`beforehand and the other components then added.
`impact polystyrene (HIPS) or ABS. To do this, the
`beforehand and the other components then added.
`impact polystyrene (HIPS) or ABS. To do this, the
`As stated above, the novel molding materials are
`vinyl-aromatic polymers are prepared in the presence of
`As stated above, the novel molding materials are
`vinyl-aromatic polymers are prepared in the presence of
`distinguished by extremely high impact strength. Com
`dist