CH617951A5 - Material based on a copolymer having a high content of nitrile structural units - Google Patents

Description

617 951

2nd

PATENT CLAIMS

1. Mass based on a copolymer with a high content of nitrile structural units from 100 parts by weight of a graft copolymer, as is by emulsion copolymerization of 50 to 95 percent by weight, based on the total amount of monomers, acrylonitrile and / or methacrylonitrile, and 50 to 5 percent by weight, based on the total amount of monomers, at least one vinyl monomer is available in the presence of a conjugated diene polymer latex, and 0.5 to 15 parts by weight of at least one of the following impact modifiers: chain-shaped polyester polymers, hydrogenated castor oil, epoxy compounds, organic phosphites, aliphatic hydrocarbons with 10 to 35 carbon atoms and liquid polymers with a molecular weight of 250 to 10,000.

2. Composition according to claim 1, characterized in that the graft copolymer is such as is obtainable by emulsion polymerization of an amount by weight of acrylonitrile and / or methacrylonitrile and vinyl monomers which corresponds to 3 to 5 times the amount by weight of the conjugated diene polymer latex.

3. Composition according to one of claims 1 or 2, characterized in that the impact modifier is a chain-shaped polyester polymer with an average molecular weight of 500 to 10,000, as can be obtained by condensation of a dibasic acid or an anhydride thereof with a glycol.

4. Composition according to one of claims 1 to 3, characterized in that the impact modifier is hydrogenated castor oil.

5. Composition according to one of claims 1 to 4, characterized in that the impact modifier is an epoxy compound with a molecular weight of 100 to

Is 10,000.

6. Composition according to one of claims 1 to 5, characterized in that the impact modifier is an organic phosphite of the following general formula

11. Composition according to one of claims 1 to 10, characterized by a graft copolymer which contains one of the following conjugated diene polymer latex as a graft base: a polybutadiene rubber latex, an acrylonitrile

• or methacrylonitrile-butadiene copolymer rubber latex or a styrene-butadiene copolymer rubber latex or a polyisoprene rubber latex.

12. Composition according to one of claims 1 to 11, characterized by a graft copolymer as it is by emulsion copo-

) Lymerisation of acrylonitrile and / or methacrylonitrile with a lower alkyl vinyl ether, a lower alkyl acrylate, styrene, a lower alkyl vinyl ketone and / or isobutylene is available as vinyl monomers in the presence of the conjugated diene polymer latex.

13. Composition according to one of claims 1 to 12, characterized in that the impact modifier is a liquid polybutadiene, a liquid butadiene-acrylonitrile copolymer or a liquid butadiene-styrene copolymer with an average molecular weight of 250 to 10,000

i is.

50

55

, where R (, R2 and R3 may be the same or different and denote hydrogen atoms or C 1-6 alkyl or aryl groups which have one or more substituents from the group halogen atoms, groups of the formulas —SH, —CN, —OH, alkyl groups or can have aryl groups.

7. Composition according to one of claims 1 to 6, characterized in that the impact modifier is an aliphatic C10_35 hydrocarbon which can be substituted by halogen atoms or groups of the formulas -SH, -CN or by aryl groups.

8. Composition according to one of claims 1 to 7, characterized in that the impact modifier is a liquid polymer with an average molecular weight of 400 to 3000. m

9. Composition according to one of claims 1 to 8, characterized by 1.0 to 5.0 parts by weight of the impact modifier per 100 parts by weight of the graft copolymer.

10. Composition according to one of claims 1 to 9, characterized in that the total amount by weight of the acrylonitrile and / or the methacrylonitrile and the vinyl monomer is 5 to 20 times the amount by weight of the conjugated diene polymer latex.

It has been proposed to improve the processability or moldability of a copolymer with a high content of acrylonitrile components by adding various additives. According to Japanese patent application number 1533/1971, a dialkyl phthalate can be added. According to Japanese patent application number 10 952/1974, a higher alcohol can be added. According to Japanese patent application number 10 953/1974, a higher alcohol and a fatty acid ester can be added.

On the other hand, it has been proposed to improve the impact resistance of such copolymers by adding an alcohol and / or an ester and / or an amide having an aliphatic hydrocarbon group having 9-32 carbon atoms (Japanese Patent Application No. 20 235/1972). The esters are partial esters or complete esters of monocarboxylic acids, dicarboxylic acids and tricarboxylic acids. Such connections differ significantly from chain-shaped polyester polymers.

It has also been proposed to improve the impact resistance of copolymers with a low content of nitrile components (so-called ABS copolymers) by adding a linear saturated polyester (Japanese Patent Application No. 34 590/1974) or an oxidized soybean oil ( U.S. Patent No. 3,725,332). However, this is an improvement in the impact resistance of an ABS copolymer with a low nitrile content, produced by a special process of substance suspension polymerization. This differs considerably from a copolymer with a high nitrile content produced by emulsion polymerization.

Copolymers of acrylonitrile and another vinyl type monomer are used as containers for food and pharmaceutical products or for packaging other materials.

It is the object of the present invention to show a composition based on a copolymer with a high content of nitrile structural units, which has excellent impact resistance, high transparency, good flowability in the melt, excellent gas impermeability, high water resistance and good resistance to devitrification tendency (haze inhibition) and good thermal stability.

This object is achieved by the mass according to claim 1.

617 951

Conjugated diene polymers which provide the basis for the graft polymers are homopolymers of conjugated dienes or copolymers of at least 50% by weight of a conjugated diene and a vinyl comonomer. As conjugated dienes e.g. 1,3-butadiene, isoprene, chloroprene or the like in question. From an economical point of view and from the point of view of polymerizability, 1,3-butadiene and isoprene are preferred. In particular, copolymers of a conjugated diene and a vinyl comonomer are suitable as copolymers of the conjugated diene.

Suitable vinyl comonomers are all those compounds which can be copolymerized with the conjugated diene latex. Acrylonitrile and methacrylonitrile can serve as comonomers for the conjugated diene polymer. It is necessary that the copolymers contain at least 50% by weight of the conjugated diene component. If less than 50% by weight of the conjugated diene component is present, the rubber elasticity of the copolymer is impaired and the graft copolymer obtainable by copolymerizing the diene and the vinyl monomer in: presence of the copolymer shows a low impact resistance. The homopolymer latex or copolymer latex is made by emulsion polymerization. The emulsion polymerization can at 0 to 100 ° C in the presence of an emulsifier such as alkylbenzenesulfonate; one: radical polymerization initiator such as potassium persulfate;

a chain transfer agent such as dodecyl mercaptan can be carried out in the aqueous phase.

The graft copolymerization is carried out in such a way that the nitrii and the vinyl monomers form the surface layer components and the conjugated diene polymer latex serves as the basis. Suitable vinyl monomers are vinyl compounds and vinylidene compounds which are copolymerizable with the nitrii. Typical vinyl monomers include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether; Acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate; aromatic olefins such as styrene, a-methylstyrene, vinyltoluene and t-butylstyrene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; 4 vinyl amides such as acrylamide, methacrylamide, N-methyl acrylamide and N-t-butyl acrylamide; N-substituted vinyl compounds such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylpyridine; halogen-containing compounds such as vinyl chloride, vinyl bro-mid, vinylidene chloride and tetrafluoroethylene; α-olefins, such as 4 isobutylene, 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1,2-ethylbutene-1.

The amounts of the nitrii and the vinyl monomer, based on the total monomers of the graft copolymerization, are 50 to 95% by weight for the nitrii and 50 to 5% by weight s for the vinyl monomer. If more than 95% by weight of the nitrile is present, the flowability of the graft copolymer in the melt is impaired. On the other hand, if less than 50% by weight of the nitrile is present, the gas impermeability of the graft copolymer is impaired. The total amounts 5 of the nitrile and the vinyl monomer are preferably 3 to 50 times the weight of the conjugated diene polymer latex, and particularly 5 to 20 times the weight of the conjugated diene polymer latex. In this case, a balance in impact resistance and moldability is achieved, f The total amount of the nitrile and the vinyl monomer can also be 1 to 3 times the weight of the conjugated diene polymer latex. In the latter case, it is preferred to mix the graft copolymer obtained with a copolymer prepared by copolymerizing the nitrile and the vinyl monomer in the absence of the conjugated diene polymer latex. The copolymerization of the nitrile and the vinyl monomer is carried out by emulsion polymerization. The emulsion polymerization can be carried out by adding the conjugated diene polymer latex to an aqueous medium and then adding an emulsifier. A sodium alkylbenzenesulfonate or a phosphate ester of polyoxyethylene alkylphenol ether or sodium alkylnaphthalenesulfonate can be used as the emulsifier. Furthermore, a radical polymerization catalyst, such as potassium persulfate, or a redox-type catalyst and other additives are added. Furthermore, the nitrii and the vinyl monomer are added and the whole is then stirred at 0 to 100.degree. The obtained graft copolymer latex is mixed with an aqueous solution of a small amount of a polyvalent inorganic salt such as aluminum sulfate or magnesium sulfate to precipitate the product. The graft copolymer is washed and dried.

The special impact modifiers of the composition according to the invention are to be explained below. Chain-shaped polyester polymers are provided as impact modifiers. These can e.g. Be polymers which can be prepared by condensation reaction of a dibasic acid, such as phthalic anhydride, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, azelaic acid or maleic anhydride with a glycol, such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, hexanedyl glycol or neopentyl. The molecular weight of the chain-shaped polyester polymer is preferably in the range of 500 to 10,000.

If the molecular weight is above 10,000, the compatibility with the graft copolymer is impaired and the processability of the composition is impaired.

Hydrogenated castor oil is also provided as the impact resistance modifier. This is obtained by hydrogenating castor oil using known methods. In particular, hydrogenated castor oils can be used according to the invention which are essentially insoluble in an alcohol at room temperature. The hydrogenation of castor oil leads to the partial formation of free fatty acid and alcohol. Such a hydrogenated castor oil with a low content of a free fatty acid and an alcohol can be used. However, if the amount of the free fatty acid and the alcohol is too high, the water resistance and the resistance to devitrification are deteriorated, and these properties are said to be improved by the addition of the hydrogenated castor oil. During the hydrogenation, hydroxyl groups of the castor oil remain, so that a high affinity for the graft copolymer is obtained, which has a favorable effect on the compatibility with the graft copolymer.

Epoxy compounds are also provided as impact modifiers. These can be compounds with an epoxy group and a molecular weight of 100 to 10,000. Typical epoxy compounds include epoxidized soybean oil and epoxidized linseed oil.

Further typical epoxy compounds are mentioned below:

ch3 (ch2) 7ch ~ c; h (ch2) 7cooch3,

o ch3 (ch2) 7ch-c; h (ch2) 7cooc8h17,

o ch3 (ch2) 4ch-chch2ch = ch (ch2) 7cooc4h9,

O cooc «Hl7

c8h17ch-ch2, o

\ / cooc8h17

617 951

: h, -chc o cht -çhch2ococh = chcooch.ch-ch,

A / "

o c8h17och- ^ h2, ch2-chch20 (ch;) 40ch2ch -ch o

o o

ch700c,

o,

ch2oco (ch2) 4cooch2s / - \

o, o o

coch2ch2oc o

o o

cooch2ch-ch,

\ / -

o cooch2ch-ch,

\ /

o cooch2chch2

cooch2chch2 o

\ /

O

-cooch2ch = ch (Ch2), ch-c; h2

o i2ch = ch (ch2) 3ch-ch2,

O

• cooch2ch = ch (ch2) 3ch-çh2

o cooch2ch-ch (ch2) 3ch = ch2,

O

. cooch2ch -ch (ch2) 3ch -çh2

\ / \ /

o o

-cooch, ch = ch (ch2) 3ch-ch2

o cooch2ch -ch (ch2) 3ch -ch2 \ / \ / cooc "" c "= ch o

cooch2ch -ch (ch2) 3ch -çh2

\ / \ /

o o cooch2ch -ch (ch2) 3c ^ -c; h2

o o ch - ch->

ch3chi o

o och-

och-

/

o och2chch -ÇHCH3

\ /

o o

II

oc (ch2) 7ch -ch (ch2) 7ch3

o o

o,

5

617 951

O'

och, ch -çhch ,, "\ / '

O

COOCHpCH -ch-,

c \ y L

O

oc (ch2) 7ch -ch (ch2) 7ch3

o cooch? ch-ch?

x (/

^ v ^ / coocho ch -ch-,

Œ

a ^ / ^ coocho ch -ch?

z \ / 2

O

och2ch -ch2

och2ch- ch2

xox ch3

-o -ch2ch - ch?

If the molecular weight is above 10,000, the compatibility with the graft copolymer is impaired and the processability of the polymer composition is impaired.

Organic phosphites, preferably those of the following general formula, are also provided as impact modifiers, where Rb R2 and R3 can be the same or different and denote hydrogen or alkyl groups having 1 to 35 carbon atoms or aryl groups. These groups can carry one or more substituents, e.g. Halogen atoms, alkyl groups, aryl groups or groups of the formulas? -SH, -CN, -OH.

At least one of the groups R ,, R2, R3 is an alkyl group with more than 4 carbon atoms or an aryl group. Typical organic phosphites are trinonylpheny] phosphite, triisodecyl phosphite, monooctadecyl phosphite, <

Di (1-bromo) hexadecyl phosphite, tri (l-bromo) octyl phosphite, (2-keto) lauryl phosphite or the like.

Furthermore, aliphatic hydrocarbons having 10 to 35 carbon atoms are provided as impact modifiers. This can be a saturated or an <unsaturated aliphatic hydrocarbon, which can carry one or more of the following groups: halogen atom, -SH, -CN, or aromatic group. Typical aliphatic hydrocarbons are decane, dodecane, penta-decane, hexadecane, eicosane, dodecatriene, hexydecatetraene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexa-decene, 1-octadecene, 1-eicosen, 1-tetracose, 1-bromo dodecane, 1-bromohexadecane, phenylpentane, 2-ketohexadecane, synthetic paraffin or the like.

Furthermore, as impact modifier liquid polymers are provided, with an average molecular weight of 250 to 10,000 and preferably 400 to 3000, which are liquid at room temperature. Typical liquid polymers are of the conjugated diene type with a low molecular weight, liquid polymers of the acrylonitrile type with a low molecular weight and other liquid polymers with a low molecular weight. Possible liquid polymers of the conjugated diene type with a low molecular weight are the homopolymers of a conjugated diene and the copolymers of a conjugated diene and a vinyl comonomer, which are used as the basis for the graft copolymerization. Particularly preferred are conjugated diene type liquid polymers having an average molecular weight of 800 to 5000. If desired, the low molecular weight conjugated diene type liquid polymer can be filtered. Liquid polymers of the acrylonitrile type with a low molecular weight are in particular liquid copolymers of acrylonitrile and / or methacrylonitrile and a vinyl comonomer. These can be the same copolymers that are formed in the preparation of the graft copolymer. Liquid copolymers of the acrylonitrile type with an average molecular weight of 300 to 2000 are particularly preferred.

617 951 6

It is particularly preferred to use liquid copolymers of the acrylonitrile type which have a low molecular weight and which have a molar ratio of acrylonitrile and / or methacrylonitrile to vinyl comonomer of 5/1 to 1/10, since in this case the compatibility is particularly good. Other liquid polymers with a low molecular weight are liquid acrylate polymers, such as butyl acrylate polymers; liquid ethylene propylene polymers; liquid epichlorohydrin polymers; liquid isobutylene polymers; liquid propylene oxide polymers; liquid halogenated butyl polymers; , “Liquid polysulfide rubber polymers such as thiocol polymers or the like. If the molecular weight of the liquid polymer is above 10,000, the compatibility with the graft copolymer is reduced.

Mixing methods for improving the properties of polymers are already known, a graft copolymer being mixed with another copolymer. However, these copolymers are solid polymers (powder or granules) which have a high molecular weight, and the required amount of the added polymer is extremely high compared to the impact modifier provided according to the invention.

If a small amount of the high molecular weight copolymer is added, the impact resistance is not significantly improved. On the other hand, if a very large amount of the high molecular weight copolymer is added, the impact resistance is deteriorated. Accordingly, high molecular weight copolymers are not suitable as impact modifiers.

The liquid polymers can be prepared by conventional polymerization of the monomers in the presence of a radical polymerization catalyst, an anionic polymerization catalyst or the like by emulsion polymerization, suspension polymerization, solution polymerization or the like. It is necessary to regulate the molecular weight during the polymerization in such a way that a liquid polymer with a low molecular weight is obtained. This molecular weight control can be carried out in various ways, e.g. by telomerization by using an active halogen compound, by using a chain transfer agent, e.g. by using a mercaptan, dipentene, terpinolene or the like,

or by adjusting the amount of the polymerization initiator. The low molecular weight polymers made by this process are liquid at room temperature. 45 Thus, these liquid polymers have excellent flowability at the temperature of molding the graft copolymer and can be uniformly dispersed in the graft copolymer. The liquid polymers can have terminal functional groups such as hydroxyl groups, such as carboxyl groups, sulfonic acid groups, epoxy groups, amino groups, thiol groups or the like.

The composition of the invention contains at least one of the impact modifiers mentioned, in an amount of 0.5 to 15 parts by weight and preferably 1.0 to 55 5.0 parts by weight per 100 parts by weight of the graft copolymer. If the amount of the impact modifier is above the above range, the compatibility of the impact modifier with the graft copolymer is lowered, and an uneven mixture is obtained, 60 and the molded product made from the polymer composition is opaque and its impact strength is lowered. In some cases, water resistance and resistance to devitrification or devitrification are also reduced. If the amount of the impact modifier is below the range (.5), the desired effect is not particularly pronounced. Various methods of admixing the impact modifier can be used. For example, the impact modifier can be added to the monomer mixture, namely the mixture of the nitrile and the Vinyl comonomers which are copolymerized in the presence of the conjugated diene polymer latex, furthermore the impact modifier can be added by latex mixing, wherein an aqueous emulsion of the impact modifier is mixed with the graft copolymer latex, furthermore, a basic mixture can first be prepared, whereby the impact modifier is added to the melted graft copolymer is obtained from the graft copolymer latex by precipitation and washing and drying the precipitate, depending on the type of impact strength its modifier can be selected. According to the invention, the impact strength of the graft copolymer can be drastically improved without the transparency, the thermal stability, the flowability in the melt and the water resistance of the graft copolymer being impaired. The effect of the impact modifier is believed to be to reduce the heterogeneity between the conjugated diene polymer and the matrix resin of the graft copolymer, so that unification is brought about. It is also believed that the impact modifier increases the physical affinity between the conjugated diene polymer and the matrix resin. If epoxy compounds are used as impact modifiers, this improves the thermal stability.

If hydrogenated castor oil is used as the impact modifier, the water resistance or watertightness and the resistance to devitrification, in particular at high temperature, are also improved. The reason for this is seen in the fact that the hydrogenated castor oil increases the affinity between the conjugated diene polymer and the matrix resin and that the hydrogenated castor oil can be fluidized at the molding temperature of the graft copolymer and that the hydrogenated castor oil is water-insoluble and is difficult to hydrolyze. The hydrogenated castor oil is uniformly dispersed in the matrix resin by melt mixing. Micropores are formed in the production of moldings from the melt. The hydrogenated castor oil now fills these micropores, so that the water resistance of the mass is improved.

The compositions according to the invention based on a copolymer of the nitrile type have excellent properties and, in particular, excellent transparency, excellent gas impermeability, good flowability in the melt or the like and excellent impact resistance. In some cases, improvements in water resistance, resistance to devitrification and thermal stability are also observed. Hollow molded articles produced from the composition according to the invention are therefore advantageously suitable as containers for foods and pharmaceuticals and for packaging various other materials.

The invention is explained in more detail below on the basis of exemplary embodiments. In these examples, all parts are parts by weight. The comparative data of copolymers without impact modifier are given in the tables.

example 1

By emulsion polymerization, 80 parts of acrylonitrile and 20 parts of methyl vinyl ether are copolymerized in the presence of 10 parts of a latex (solid component) of a butadiene-acrylonitrile copolymer (70 parts of butadiene and 30 parts of acrylonitrile), whereby a graft copolymer powder is obtained. 100 parts of this graft copolymer are each added to the chain-shaped polyester polymer according to Table 1 in the amounts specified therein. The mixture is at 190 ° C

7

617 951

kneaded for 5 minutes at 60 rpm in a Brabender plastograph. The copolymer composition obtained is subjected to a pressure molding process at 200 ° C. under a pressure of 150 kg / cm 2 for 8 minutes, whereby a molded product with excellent transparency is obtained. The results of the measurements of the Izod impact strength at 20 ° C are summarized in Table 1.

Table 1

Test chain-shaped amount of Izod impact strength

No. polyester poly (parts) (notch) (kg-cm / cm2)

meres

1

none

0

14-15

2nd

A type

1.0

88

3rd

A type

3.0

> 110

4th

B type

1.0

85

5

B type

3.0

108

6

C type

1.0

91

7

C type

3.0

> 110

8th

D type

1.0

78

9

D type

3.0

101

Molecular weight

A type: neopentyl glycol ester of phthalic acid 600 B type: propylene glycol ester of adipic acid 1 000 C type: 1,3-butene glycol ester of adipic acid 2 000 D type: glycol ester of sebacic acid 8 000

Example 2

By emulsion polymerization, 80 parts of acrylonitrile and 20 parts of methyl vinyl ether are copolymerized in the presence of 15 parts of a latex (solid component) of a butadiene-methyl acrylate copolymer (71.5 parts of butadiene and 28.5 parts of methyl acrylate), whereby a graft copolymer is obtained . To this graft copolymer is added a chain-shaped polyester polymer (A type) in an amount of one part or 2 parts based on 100 parts of the graft copolymer. The mixture is processed in a Brabender plastograph according to Example 1. The Izod impact strength of the products at 20 ° C, 10 ° C or 0 ° C is given in Table 2.

The amount of one part or 2 parts based on 100 parts of the graft copolymer was added. The mixture is kneaded in a Henschel mixer and pelletized by extrusion at 190 ° C. The pellets obtained are used for blow molding with an injection molding extruder. A bottle with an internal volume of 500 ml and a weight of 25 g is produced. The bottle is filled with an aqueous solution of sodium chloride cooled to 100 ° C and then dropped vertically. It is determined whether the bottle breaks. The drop height at which half of the bottles break is determined. If the chain-shaped polyester polymer is not added, this is 2 m. If part of the chain-shaped polyester polymer of the A type is added, the drop height is 6 m. When 2 parts of the A-type polymer are added, none of the samples break. Furthermore, the oxygen permeability of the bottles is measured at 30 ° C, with 0% internal moisture and less than 20% external moisture.

Test No. 13 14 15

Chain-shaped polyester polymer (parts) 1.0 2.0 0

25th

Oxygen permeability

(cm3 / m2 • day ■ atm.) 2.1 2.2 2.4

M

Example 4

An emulsion polymerization of 80 parts of acrylonitrile and 20 parts of methyl vinyl ether are carried out in the presence of 10 parts of latex (solid component) of a 15-butadiene-acrylonitrile copolymer (70 parts of butadiene and 30 parts of acrylonitrile), with one part of a chain-like mixture being added to 100 parts of the monomer mixture Polyester polymers (B type) are used. The Izod impact strength of a molded article produced therefrom at 20 ° C. is given below.

4 (1

Test No. 16 17

Chain-shaped polyester polymer (parts) 1.0 0

45

Izod impact strength (notch)

(kg-cm / cm2) 80 20

Table 2

Test chain-like amount of Izod impact strength like this

No. polyester poly (parts) (notch) (kg-cm / cm2) Example 5

meres An emulsion polymerization of 80 parts of acrylic

20 ° C 10 ° C 0 ° C nitrii and 20 parts of ethyl vinyl ether in the presence of 10 parts of a latex (solid component) of a butadiene-acrylonitrile

10th

none

0

15

9

3rd

55 copolymers (70 parts butadiene and 30 parts acrylonitrile) were carried out, a graft copolymer latex being obtained.

11

A type

1.0

105

94

76

An emulsion of the chain-shaped polyester polymer (the

Ratio of the chain-shaped polyester polymer: emulsified

12

A type

2.0

> 110

97

86

gate: water is 2: 1: 10; Emulsification in a homogen

(, O nizer) is added to the graft copolymer in an amount of one part, calculated as chain-shaped example 3 polyester polymer, per 100 parts of the graft copolymer. The

An emulsion polymerization of 80 parts of acrylic mixture is precipitated and dried, a polymer nitrile and 20 parts of methyl vinyl ether being obtained in the presence of 12.5 powder. The Izod impact strengths of the molded parts latex (solid component) of a butadiene-acrylonitrile product at 20 ° C. are summarized in Table 3. Copolymers (75 parts butadiene and 25 parts acrylonitrile)

carried out, whereby a graft copolymer powder is obtained.

The A-type chain-shaped polyester polymer is in one

617 951

8th

Table 3

Test chain-like quantity

No. polyester polymer (parts)

18 A type 1.0

19 B-type 1.0

Example 6

An emulsion polymerization of 24 parts of acrylonitrile and 6 parts of methyl vinyl ether is carried out in the presence of 15 parts of a latex (solid component) of a butadiene-acrylonitrile copolymer (70 parts of butadiene and 30 parts of acrylonitrile), a graft copolymer latex being obtained. To this graft copolymer latex is added a latex of a copolymer which has been prepared by emulsion polymerization of 56 parts of acrylonitrile and 14 parts of methyl vinyl ether (polymer of the non-conjugated diene type). The mixing is carried out well and mixed with an aqueous solution of aluminum sulfate. The precipitate is washed with water and dried to give a polymer powder. Two parts of the chain-shaped polyester polymer (B type) are added to 100 parts of the polymer powder. The Izod impact strength of a molded article produced therefrom at 20 ° C. and 0 ° C. is given below.

Test No. 20 20 ° C 0 ° C

(70 parts butadiene and 30 parts styrene) is carried out

whereby a graft copolymer is obtained. In each case a chain-shaped polyester polymer according to Table 5 is added to 100 parts of the graft copolymer in the amounts specified therein. The mixture is processed according to Example 1. The Izod impact strengths of the products at 20 ° C are summarized in Table 5.

Table 5

i "Test chain-shaped amount of Izod impact strength

No. polyester polymer (parts) (notch on the back)

(kg-cm / cm2)

26-29

59 94

48

77

49 70

45

78

Izod impact strength (notch) (kg-cm / cm2)

95

91 •

none

0

Type A

1.0

Type A

3.0

TypeB

1.0

TypeB

3.0

Type C

1.0

TypeC

3.0

Type D

1.0

TypD

3.0

30th

none

0

31

Type A

1.0

32

Type A

3.0

33

TypeB

1.0

34

TypeB

3.0

35

TypeC

1.0

36

TypeC

3.0

37

TypD

1.0

38

TypD

3.0

Izod impact strength (notch)

(kg-cm / cm2)> 110 58

Example 7

An emulsion polymerization of 75 parts of acrylonitrile and 25 parts of methyl acrylate is carried out in the presence of 10 parts of a latex (solid component) of a butadiene-acrylonitrile copolymer (70 parts of butadiene and 30 parts of acrylonitrile), a graft copolymer being obtained. In each case the chain-shaped polyester polymer according to Table 4 is added in the amounts specified there to 100 parts of the graft copolymer obtained. The mixtures are processed further in accordance with Example 1. The Izod impact strengths of the products at 20 ° C are summarized in Table 4.

Table 4

Chain-like quantities test of Izod impact strength

No. polyester polymer (parts) (notch) (kg-cm / cm2)

21st

none

0

11-13

22

Type A

1.0

35

23

Type A

3.0

54

24th

TypeB

1.0

33

25th

TypeB

3.0

48

26

TypeC

1.0

42

27th

TypeC

3.0

66

28

TypD

1.0

31

29

TypD

3.0

50

Example 8

An emulsion polymerization of 70 parts of acrylonitrile and 30 parts of styrene in the presence of 10 parts of a latex (solid component) of a butadiene-styrene copolymer

Example 9

An emulsion polymerization of 80 parts of acrylonitrile and 20 parts of methyl vinyl ketone is carried out in the presence of 10 parts of a latex (solid component) of a butadiene-acrylonitrile copolymer (70 parts of butadiene and 30 parts of acrylonitrile), a graft copolymer being obtained. The mixture is processed according to Example 1. The Izod impact strengths of the products at 20 ° C are summarized in Table 6.

Amount of Izod impact strength (parts) (notch) (kg-cm / cm2)

0 10

1.0 31

3.0 66

1.0 35

3.0 71

Example 10

An emulsion polymerization of 80 parts of acrylonitrile and 20 parts of isobutylene in the presence of 15 parts of a latex (solid component) of a butadiene-acrylonitrile copolymer (70 parts of butadiene and 30 parts of acrylonitrile) r, ii is carried out, giving a graft copolymer . The chain-shaped polyester polymer according to Table 7 is added to the 100 parts of the graft copolymer in each case in the amounts specified therein. The mixtures are processed further in accordance with Example 1. The Izod impact strength values of the products m at 20 ° C are given in Table 7.

4o Table 6

Text chain-shaped no. Polyester polymer

39 none

40 Type A

41 Type A

5o 42 type B

43 Tvdb

9

617 951

Table 7

Test chain-like quantity

No. polyester polymer (parts)

Izod impact strength (notch) (kg-cm / cm2)

44

none

0

21st

45

Type A

3.0

84

46

TypD

3.0

79

Example 11

The process according to Example 1 is repeated, using hydrogenated castor oil instead of the chain-shaped polyester polymer, one part or three parts per 100 parts of the graft copolymer. The hydrogenated castor oil has a melting point of 85 to 87 ° C, an acid value of less than 2.0, a saponification value of 175 to 185 and an iodine value of less than 1.5. The mass obtained is pressed, giving a pressed sample with excellent transparency (thickness 0.65 mm). To test the water resistance and the devitrification resistance, the solid sample is placed in hot water at 50 ° C. for 100 hours or in hot water at 80 ° C. for one hour and then removed and air-dried. The haze of the pressed sample is measured with a haze meter (SEP-H, manufactured by Nippon Seimitsu Kogaku K.K.). The Izod impact strength values of the samples are also measured at 20 ° C. The results are summarized in Table 8.

Table 8 clearly shows that adding hydrogenated castor oil not only improves the impact resistance, but also the resistance to devitrification.

s Example 12

The process according to Example 3 is repeated, but using instead of the chain-shaped polyester polymer, hydrogenated castor oil according to Example 11, one part or 2 parts per 100 parts of the polymer mixture. A bottle is produced from the granules obtained by blow molding. The strength in the vertical drop test (drop height at which half of the bottles break) and the oxygen permeability of the bottles are measured according to Example 3. The bottles are filled with hot water at 50 ° C and kept in a vessel at 50 ° C for 100 hours. Then part of the wall of the bottle is cut out and the fog of the sample is measured according to Example 11. The results are summarized in Table 9.

2o Table 9

Table 8 Test Amount of No. Hydrogenated

Veil (%)

Izod impact strength (notch)

Castor oil (parts)

50 ° C / 100 h

80 ° / lh

(kg-cm / cm2)

47

0

35

85

14-15

48

1.0

18th

27th

70

49

3.0

10th

21st

110

test

Amount of

strength

oxygen

Veil-

No.

hydrogenated at permeability value (%)

Castor oil vertical

(cm3 / m2 day

(Parts)

Drop test

Atm)

50

0

1.5

2.2

33

51

1.0

3.0

2.3

16

52

2.0

5.0

2.3

11

From Table 9 it can be clearly seen that the addition of hydrogenated castor oil improves the strength in the vertical drop test as well as the resistance to devitrification, without this being associated with an increase in oxygen permeability.

Example 13

The process according to Example 1 is repeated, the 40 epoxy compounds according to Table 10 being used instead of the chain-shaped polyester polymer, in each case in the amounts given in Table 10 per 100 parts of the graft copolymer. The mold products obtained show excellent transparency. The Izod impact strength values and the coloration levels (% transmittance at a 45 wavelength of 400 m [i) of the products are given in Table 10.

Table 10

Test epoxy compound no.

Quantity Izod impact coloration (parts) strength T 400 (%) (notch)

(kg-cm / cm2)

53

no

0

15

31

54

Epoxidized soy

1.0

67

40

55

(Oxirane oxygen%:> 7.0)

3.0

> 110

45

56

Epoxidized linseed oil

1.0

70

35

57

(Oxirane oxygen%:> 9.0)

3.0

> 110

41

58

CH3 (CH2) 7CH-CH (CH2) 7COOC4H9 \ /

1.0

62

37

59

do.

3.0

104

44

617 951

10th

Test epoxy compound no.

60 CH3 (CH2) 4CH-CHCH2CH = CH (CH2) 7COOC4H9

O

Quantity Izod impact coloration (parts) strength T 400 (%) (notch)

(kg-cm / cm2)

1.0 58

39

61

do.

3.0 101

50

62 C8H17CH-CH2

\ /

O

2.0

82

63 C8H17OCH2CH-CH2

O

2.0

90

64

65

66

CH2CHCH20 (CH2) 40CH2CH-CH2

V \ /

2.0 80

O

x>

COOCH2CH = CH (CH2) 3 CH-CH2

O

COOCH2CH = CH (CH2) 3 CH-CH2

O

Table 10 clearly shows that the impact resistance and the degree of coloration of the products are considerably improved by adding the epoxy compound. This shows that the products have high thermal stability.

2.0

2.0

74

91

• in test epoxy compounds quantity Izod impact strength no. (Parts) (notch) (kg-cm / cm2)

20 ° C 10 ° C 0 ° C

Example 14 45

The process according to Example 2 is repeated, but using the epoxy compound according to Table 11 instead of the chain-shaped polyester polymer, namely the amount stated in this table per 100 parts of the graft copolymer. Press-molded products are obtained whose Izod impact strength values are measured at different temperatures. The results are summarized in Table 11.

Tables test epoxyver no. bonds

10 67

no

Epoxidized soybean oil (oxirane oxygen%:

More than 7.0)

Amount of Izod impact strength (parts) (notch) (kg-cm / cm2)

1.0

20 ° C 15

72

10 ° C 9

48

0 ° C 3

31

55

69 Epoxidized

Butyl stearate 1.0 68 43 33

70 do. 2.0 101 76 58

Example 15

The procedure of Example 3 is repeated, using epoxidized soybean oil (oxirane oxygen%: more than 7.0) instead of the chain-shaped polyester polymer, one part or 2 parts per 100 parts of the polymer mixture. A bottle is produced from the pellets obtained by blow molding. Furthermore, a press mold product is produced from the pellets by press molding. The Izod impact strength of the molded product at 0 ° C. and the strength of the bottle in the vertical drop test and the oxygen permeability of the bottle are measured in accordance with Example 3. The results are summarized in Table 12.

68 do.

2.0

105

85

67

11

617 951

Table 12 Test amount of epoxidized soy

No.

Izod impact strength Oxygen resistance at permeability (notch) vertical (cm3 / m2 day (kg-cm / cm2) drop test (m) atm)

71 0

72

73

1.0

2.0

35 71

5

> 6

2.4

2.2

2.3

Test epoxyver no. binding

80 Epoxidized butyl stearate

Amount of Izod-Schiag stain (part) strength grad

(Notch on T400 (%)

Back)

(kg-cm / cm2)

81

Table 12 clearly shows that the strength of the vertical drop test (drop height at which half of the bottles break) is significantly improved by adding the epoxidized soybean oil without an increase in oxygen permeability.

Example 16

The process according to Example 7 is repeated, but using the: o epoxy compound according to Table 13 in the amount specified there instead of the chain-shaped polyester polymer. A molded product is obtained. The Izod impact strength at 20 ° C and the degree of coloration of the product are summarized in Table 13.

C8H17CH-CH2 O

2.0 2.0

71 65

81

78

Example 18

The process according to Example 1 is repeated, using the impact modifier according to Table 15 in the amount specified there instead of the chain-shaped polyester polymer. A molded product is obtained whose Izod impact strength is measured at 20 ° C. The results are summarized in Table 15.

Table 15

Test impact strength no. modifier

Amount of Izod impact strength (parts) (notch)

Table 13

(kg-cm / cm2)

Epoxy test

amount

Izod blow

Coloring

No tie

(Parts)

strength degree

1

none

0

14-15

(Score)

T 400 (%)

(kg-cm / cm2)

3o 82

Trinonylphenyl phosphite

1.0

66

83

do.

3.0

98

74 none

0

14

39

84

Trilauryl phosphite

1.0

55

75 epoxidized

85

do.

3.0

81

Soy

35

(Oxirane acid

86

Dilauryl phosphite

1.0

53

fabric%:> 7.0)

2.0

47

58

87

n-dodecane

1.0

58

76 Epoxidized

88

do.

3.0

79

Butyl stearate

2.0

51

51

40

89

n-hexadecane

1.0

61

77 C8H, 7CH-CH,

2.0

55

45

\ /

n

90

n-eicosan

1.0

55

45 91

1-dodecene

1.0

63

Example 17

The process according to Example 8 is repeated, using the epoxy compound given in Table 14 in the amount given there instead of the chain-shaped polyester polymer. A molded product is obtained, the Izod impact strength of which is measured at 20 ° C. and the degree of coloration. The results are summarized in Table 14.

Table 14 Test epoxyver no. binding

55

Amount of Izod impact coloring (parts) strength grad

(Notch on T400 (%)

Back)

(kg-cm / cm2)

Example 19

The process according to Example 2 is repeated, using the impact modifier according to Table 16 in the amount specified there instead of the chain-shaped polyester polymer. A molded product is obtained. The Izod impact values of this product at various temperatures are shown in Table 16.

Table 16

Impact mode test - Amount of Izod impact strength

78

79

no

0

Epoxidized soybean oil (oxirane oxygen%: 2.0

More than 7.0)

26-29

58

75

80

No finishing agent

60

10 none f'5 92 trilauryl phosphite

93 n-dodecane

(Parts) (notch)

(kg-cm / cm2)

20 ° C 10 ° C 0 ° C

0

15

9

3rd

3.0

96

67

55

3.0

81

53

28

617 951

12

Example 20

The process according to Example 4 is repeated, one part of trinonylphenyl phosphite being used per 100 parts of the monomer mixture instead of the chain-shaped polyester polymer. A polymer powder is obtained. The Izod impact strength (notch) of a molded product produced therefrom is 51 kg-cm / cm2 at 20 ° C. (test no. 94).

Example 21

The process according to Example 5 is repeated, with one part of n-dodecane being used per 100 parts of the graft copolymer instead of the chain-shaped polyester polymer. A molded product is obtained, the Izod impact strength (notch) of which is 65 kg-cm / cm 2 at 20 ° C. (Test No. 95).

Table 19

Low Amount Molecular Weight Liquid Polymer Test (Parts)

1 none

102 Liquid polybutadiene io (M.G. 1,500)

103 do.

Example 22

The process according to Example 7 is repeated, using the impact modifier according to Table 17 instead of the chain-shaped polyester polymer. A molded product is obtained, the Izod impact strength of which is given in Table 17 at 20 ° C.

Table 17

Impact resistance test - quantity no. Decorative agent (parts)

21 none

0

96 trinonylphenyl phosphite 1.0

97 do. 3.0

98 n-dodecane

2.0

Izod impact strength (notch)

(kg-cm / cm2)

11-13

41 62

45

109

30th

110

111

112

1.0 3.0

104 Liquid butadiene-acrylonitrile copolymer (weight ratio 70:30) 1.0

15 (M.G. 1,900)

105 do. 3.0

106 Liquid butadiene-styrene copolymer (weight ratio 70:30) 1.0 (M.G. 1,400)

107 Liquid butadiene-methyl acrylate copolymer (weight ratio 69:31) (M.G. 2,100) 1.0

25 108 do.

3.0

Liquid acrylonitrile methyl vinyl ether n-dodecyl mercaptan copo

lymeres (mol. ratio 2: 1: 1) 1.0 (M.G. 400)

do. 3.0

do. 4.0

35

Liquid acrylonitrile-methyl acrylate-n-dodecyl mercaptan copolymer (mol. Ratio 2: 2: 1) (M.G. 700) 1.0 do. 3.0

Example 23

The procedure of Example 8 is repeated, using 113 instead of the chain-shaped polyester polymer

Impact resistance modifier according to Table 18 in which there 114 liquid acrylonitrile-styrene-n-

specified amount. A molded product is obtained, 40 dode-cylmercaptan copolymer whose Izod impact strength at 20 ° C. is given in Table 18 (mol ratio 1: 3: 1) (M.G. 600) 1.0

is. 115 do. 3.0

Izod impact strength (notch) (kg-cm / cm2)

14-15

66 75

59 72

54

62 77

35

83 103

40 89

32 67

Table 18 Test impact strength modi amount

No ornamental

116 Liquid AcryInitrile-2-Ethyl Ihexyl Izod Impact Resistance 45 Acrylate Copolymer (Molverh.

(Parts) (notch)

(kg-cm / cm2)

30 none 0 26-29

99 trinonylphenyl phosphite 3.0 59

100 n-dodecane 2.0 44

101 n-hexadecane 2.0 47

Example 24

The process according to Example 1 is repeated, using the liquid polymer of low molecular weight given in Table 19 in the amount indicated there instead of the chain-shaped polyester polymer. A molded product with excellent transparency is obtained. The Izod impact strength of the product at 20 ° C is given in Table 19.

117

1: 1) (M.G. 1,000) do.

1.0 3.0

50

41 93

Example 25

The process according to Example 4 is repeated, but 3.0 parts of a liquid acrylonitrile-methylvinyl ether-n-dodecyl-55 mercaptan copolymer (molar ratio 2: 1: 1) (molecular weight about 400) per 100 parts of the instead of the chain-shaped polyester polymer Monomer mixture. A molded product is obtained whose Izod impact strength at 20 ° C. (notch) is 90 kg-cm / cm 2 (test No. 118).

60 Example 26

The process according to Example 7 is repeated, but instead of the chain-shaped polyester polymer, the amount of a liquid acrylonitrile-methylvinyl ether-n-dodecyl mercaptan copolymer (Molver 65 ratio 2: 1: 1) (molecular weight about 400) given in Table 20 is used. The Izod impact strength of the mold products obtained at 20 ° C. is shown in Table 20.

13

617 951

Table 20

Test Amount of Liquid No. Copolymers (Parts)

21st

119

120

0

1.0

3.0

Izod impact strength (notch) (kg-cm / cm2)

11-13

28

52

Example 27

The process according to Example 8 is repeated, using 3.0 parts of the liquid copolymer according to Example 26 instead of the chain-shaped polyester polymer. A molded product is obtained whose Izod impact strength at 20 ° C. (notch on the back) is 71 kg-cm / cm 2 (test No. 121).