DE1119508B - Thermoplastic, impact-resistant molding compounds - Google Patents

Description

The main patent has impact-resistant molding compounds made from rubber-like, elastic copolymers Butadiene with acrylonitrile and thermoplastic copolymers made of acrylonitrile with styrene are the subject matter, wherein the elastic component of the applied in an amount of about 10 to 75 parts Mixture in addition to about 5 to 45 percent by weight of acrylonitrile with about 0.1 to 20 percent by weight Acrylonitrile and butadiene copolymerizable, carbonyl groups, in particular carboxyl, carbonamide and / or aldehyde groups, containing compounds and the thermoplastic component with a content of about 5 to 45 weight percent acrylonitrile in these mixtures in an amount of 90 to 25 parts is included. These mixtures with elastic components containing carbonyl groups have compared to the corresponding mixtures, in which the elastic component does not have any Carbonyl groups has significant advantages. The copolymers containing carbonyl groups have the property of self-crosslinking of the copolymers through brief treatment to cause elevated temperatures between about 100 and 220 ° C. They also enable manufacturing uniform mixtures with the thermoplastic copolymers by mixing the at the Emulsion polymerization resulting latexes.

In a further development of the invention it has now been found that elastic components for the said Mixtures generally such rubber-like 30 or Copolymers are suitable which consist of 25 to 90 percent by weight of a styrene-acrylonitrile copolymer (55:45 to 95: 5) and on the other hand 10 to 75 percent by weight of a rubber elastic There are butadiene-acrylonitrile copolymers, which in addition to butadiene and 5 to 45 percent by weight Acrylonitrile still 0.1 to 20 percent by weight of a third, self-crosslinking monomer component included in polymerized form.

Self-crosslinking monomer components are understood here to mean those compounds which allow crosslinking of the copolymers at elevated temperatures. Such monomer components, which contain self-crosslinking groups are those compounds which contain N-methylolcarbonamide groups, etherified N-methylolcarbonamide groups, dioxolane groups, ureido groups or 2-methylene-1,3-dioxo radicals of the formula

COR ₄

Thermoplastic, impact-resistant molding compounds

Addendum to patent 1053 779

Applicant:

Paint factories Bayer Aktiengesellschaft,
Leverkusen-Bayerwerk

Dr. Wilhelm Graulich, Dormagen,
Dr. Gottfried Scriba, Leverkusen,
and Dr. Paul Schneider, Opladen,
have been named as inventors

have, in which R ₄ and R _{5 denote} a hydrocarbon radical which can also be bonded to the carbonyl group via an oxygen bridge.

Copolymerizable monomers which introduce these groups into the copolymers come into question are z. B.

1. Monomers that make up the grouping
-OC-N-CH ₂ OH

-OC-N-CH ₂ OR

in which R _{1 is} hydrogen, alkyl or aryl and R _{2 is} alkyl, one or more times in the molecule. Such monomers are e.g. B. the alkyl ethers of the methylol compound of acrylamide, methacrylamide, or the diamide of fumaric acid (cf.

Belgian patent 539 963).

2. Monomers that contain one or more dioxolane radicals, such as. B. Compounds of the formula

= C - COOCH »• CH - CH ₂

, c:

¹ COR _n

R ₁ R ₂

in which R = H or alkyl, R ₁ and R ₂ = H or a hydrocarbon radical, preferably alkyl.

109 749/586

3. Compounds containing at least one ureido group of the formula

-NR ₂ -CO-NHR ₂

in which R _{2 represents} H or a hydrocarbon radical. Examples of such connections are z. B. Compounds of the following formulas

a) CH ₂ = CR-COO-A-NH-CO-NH ₂
in which R is H or alkyl and A is an alkylene group, such as ζ. Β. Ethylene, propylene, isopropylene (see U.S. Patent 2,694,695).

b) CH ₂ = CH-OA-NR ₃ -CON-HR ₃
in which A is a cycloalkylene group or an alkylene group having 2 to 18 carbon atoms and R _{3 is} an aliphatic or cycloaliphatic radical having 1 to 24 carbon atoms (cf. U.S. Patents 2,694,695 and 2,734,891 and French Patent 1,075,898).

4. Compounds of the formula

COR ₄

CH ₂ == C _v

COR ₅

in which R ₄ and R _{5 denote} a hydrocarbon radical which can be the same or different and which can also be bonded to the carbonyl group via an oxygen bridge. There come z. B. in question the methylene derivatives of malonic esters, acetoacetic esters, acrylic acetic esters, acylacetones, such as. B. acetylacetone. These compounds can e.g. B. can be obtained by using compounds of the general formula

CORo

CH ₉

35

in which R ₃ and R _{4 have} the meaning given above, heated with paraformaldehyde in the presence of activated fuller's earth, the water formed is distilled off azeotropically and the reaction mixture is then worked up in a known manner.

It is also possible to subsequently convert the self-crosslinking groups into suitable copolymers to introduce, in which one z. B. copolymers containing carbonamide groups subsequently with formaldehyde, optionally in the presence of alcohols to react, methylol or methylol ether groups containing copolymers are obtained.

The copolymers are produced by the customary methods of emulsion polymerization. In addition to the monomers mentioned, it is possible to include further copolymerizable components in the copolymers Polymerize compounds. Homologues or derivatives of butadiene can also be used instead of butadiene.

The above monomers are used in the copolymer serving as the elasticizing component of butadiene and acrylonitrile in amounts of 0.1 to 20%, but preferably 1 to 10%, incorporated. In addition, crosslinking monomers (divinylbenzene, glycol diacrylate etc.) be present in small quantities. However, they do not bring about any significant improvement the physical values of the claimed polymer mixtures. These mixtures set themselves together from 10 to 75 parts of the elasticizing component, the acrylonitrile content between 5 and 45% can vary and 90 to 25 parts of the thermoplastic copolymer of acrylonitrile and styrene with a nitrile content of 5 to 45%.

The mixing and crosslinking of the components is preferably carried out according to the method of the main patent, by mixing the latexes obtained by the process of emulsion polymerization, then coagulated and the coagulum obtained are homogenized after drying for a short time at about 130 to 22O ⁰ C.

In the following examples the parts given are parts by weight.

example 1

300 parts of a copolymer are placed on a rolling mill, the rollers of which are heated to 160.degree from 65 percent by weight butadiene and 35 percent by weight acrylonitrile with a Defow value of 1200 / 34.0 over a period of 85 minutes with occasional incisions in the surrounding fur treated. It then shows a proportion of 65% insoluble in methyl ethyl ketone within 10 minutes add 700 parts of an acrylonitrile-styrene copolymer to the pretreated copolymer on the roller with 24.8 percent by weight acrylonitrile of an Instrinsic viscosity 1.3 and 100 parts titanium dioxide admitted. Test specimens produced from this mixture show the mechanical properties specified under 1, a) Values.

If, on the other hand, a copolymer of 61% butadiene, 36% acrylonitrile and 3% methylene acetylacetone with a Defo value of 2000 / 35.0 is used instead of the butadiene-acrylonitrile copolymer mentioned, then after a rolling time of only 12 minutes a 61% ^m methyl ethyl ketone insoluble material. If 700 parts of the above-described styrene-acrylonitrile copolymer and 100 parts of titanium dioxide are then mixed in in a further 10 minutes, a material having the properties specified under 1, b) is obtained.

Tabel 1 Elasticizing agent b) Mixed polymer Butadiene Mechanical properties of the mixtures a) + Acrylic
nitrile
4- methylene
acetyl acetone Butadiene
+ Acrylic
nitrile 100.5 102 40 Impact resistance 11 (kgcm / cm ² ) 42 710 Notched impact strength 11 490 (kgcm / cm ^a ) 685 380 at 20 ^° C 510 at O ⁰ C 400 Flexural strength (kg / cm ² ) .. Compressive strength (kg / cm ² ) .. Tensile strength (kg / cm ² )

Example 2

1000 parts of a 30% latex, obtained by emulsion polymerization of butadiene with 35 parts

5 6

weight percent acrylonitrile and 0.5% divinylbenzene This leads to a molding composition with the following

from defow value 1100 / 37.0, with 2058 parts properties:

of the 34% latex of a copolymer

Styrene with 20.5 acrylonitrile of the Instrinsic viscosity labeile 5

1.15 mixed. The ratio of elastic to 5 impact strength (kgcm / cm ² ) 102

thermoplastic component is then 30:70. According to notched impact strength (kgcm / cm ² )

the addition of 150 parts of titanium dioxide in the form at 20 ° C 40

a suitable aqueous dispersion that is 6 5 at 0 ° C

Mixture coagulated by saline, the Koagu-. _ ,. ".,". " , 7 ", '"'. "J

lat separated, washed salt-free and at 90 ^° C. flexural strength (kg / cm ² ) 729

dried. The dried material has a compressive strength (kg / cm ² ) 448

homogenized at 165 ⁰ C heated rolling mill, in tensile strength (kg / cm ²⁾ 407

Strips peeled off and crushed on a hammer mill; it then shows those listed under 2, a)

Values. 15 Example 4

If, however, the above is used instead of the analogue to Example 3, 967 parts of the 31% strength are obtained

set elastic component according to the invention with latex of a copolymer of butadiene

915 parts of a 32.8% latex made by mixed 35% acrylonitrile and 3% methacrylic acid-jß-ureido-

Polymerization of butadiene with 35% acrylonitrile ethyl ester from Defowert 1600 / 44.0 with 1892 parts

and 3% methylene acetoacetic ester with a Defo value of 1500/20 of a 37% copolymer latex of styrene

39.2 was obtained in emulsion, 20.7% acrylonitrile and an intrinsic viscosity are obtained

mixed and worked up to a material of 1.2 in the manner described above. The dried one

of the values listed under 2, b). Powders are mixed on a suitable internal mixer

150 parts of titanium dioxide mixed in and the pigment

Table 2 25 based mixture as previously described, granulated.

Mechanical properties of the mixtures ^{Es 2} ^ the following test results:

Impact resistance
(kgcm / cm ² )

Notch toughness
(kgcm / cm ² )

at 20 ^° C

at 0 ⁰ C

Flexural strength (kg / cm ² ) ..
Compressive strength (kg / cm ² ) ..
Tensile strength (kg / cm ² )

Elasticizing agent
Mixed polymer

a)

Butadiene
+ Acrylonitrile

+ Divinylbenzene

104

12th
6th

640
460
380

b)

Butadiene
+ Acrylonitrile

+ Methylene acetate vinegar
ester

103

45
7th

701
440
378

It follows from this that the claimed method is aimed at obtaining optimal values made possible in the shortest possible time.

Example 3

Similar to example 2, the latices of an elastic and a thermoplastic component and an aqueous dispersion of titanium dioxide mixed, namely 923 parts of a 32.5% copolymer latex of butadiene with 35.5% acrylonitrile and 3% of methaerylamide-N-methylolmethylether from Defowert 1900/45, to 1892 parts of a 37% latex of styrene with 20% acrylonitrile with a Instrinsic viscosity of 1.15 and further 100 parts of titanium dioxide in aqueous dispersion. The mixture is precipitated as in Example 2, washed and dried. The crumb coagulate obtained is in a gelled twin-screw injection molding machine heated to 170 ° C. and injected in the form of a tape, which after can be granulated technically customary process.

Table 4

Impact Resistance (kgcm / cm ² ) 89

Notch impact toughness (kgcm / cm ² )

at 2O ⁰ C 40.2

at 0 ^° C 15.7

Flexural Strength (kg / cm ² ) 650

Compressive Strength (kg / cm ² ) 470

Tensile strength (kg / cm ² ) 360

Example 5

If the latex is used instead of the elastic component described in Example 4 Copolymer of butadiene with 35% acrylonitrile and 3% jS-ureidoethyl vinyl ether of one Defo value of 1900/41 and otherwise proceeds exactly as in the previous example, this leads to a Molding compound with the mechanical values described below:

Table 5

Impact resistance (kgcm / cm ² ) 92

Notched impact toughness (kgcm ² / cm ² ) at 20 ° C 38

^at °° ^{C 14}

Flexural Strength (kg / cm ² ) 660

Compressive strength (kg / cm ² ) 450

Tensile Strength (kg / cm ² ) 370

Example 6

1000 parts of the 30% latex of a copolymer of butadiene with 35% acrylonitrile and 2% of an ester of methacrylic acid and 4-oxy-l, l-dimethyldioxolane of the Defowert 900 / 34.5 were with 1892 parts of the 37% latex of a copolymer of styrene mixed with 20% acrylonitrile and worked up as described in Example 2. That

Claims (1)

7 8 dried coagulate was then treated on a rubber-elastic butadiene-acrylonitrile mixing roller mill for 10 minutes at 160 ° C., in polymerisates that were drawn off in addition to butadiene and 5 bis strips and then to give a granulate 45 weight percent acrylonitrile 0.1 to 20 Crushed. With the help of an injection molding machine, weight percent of a third monomer component was polymerized into 240G test specimens with the following mechanical properties, which were produced at increased temperature properties: a cross-linking of this rubber-elastic, ternary copolymer, according to patent labelle 6 1,053,779, characterized in that the Mold impact strength (kgcm / cm2) 97 mass as a rubber-elastic ternary mixed notched impact strength (kgcm / cm2) 10 polymer b) contains a polymer which, as a third monomer component at 200C, contains 36 polymeric compounds, the N-methylolcarbonamide- , ver _. . ., '. ",', ',' 1 have ethereal N-methylolcarbonamide, dioxolane, Urei flexural strength (kg / cm2) 690 do_ or 2-methylene-1,3-dioxo residues. Compressive strength (kg / cm2) 478 15 2. A method for producing a molding compound tensile strength (kg / cm2) 362 according to claim 1, characterized in that the mixture of the elastic, self-crosslinking groups traSendei1 components with the thermoplastic copolymer of acrylonitrile and 1. Thermoplastic, impact-resistant molding compounds, 20 styrene over those used in emulsion polymerization consisting of a) 25 to 90 percent by weight of a latex obtained and that the dried Styrene-acrylonitrile copolymer (55:45 to mixed coagulate briefly under the action of 95: 5), and b) 10 to 75 weight percent of a shear is heated to about 130 to 220 ⁰ C. © 109 749/586 12.61