DE2653145A1 - MOLDING - Google Patents

Description

Thermoplastic molding compounds made from acrylonitrile-butadiene-styrene polymers and dihydric phenol polycarbonates are known. Their thermal stability and resistance to weathering are but in need of improvement. The object of the present invention was therefore to find thermoplastic molding compositions without them To create defects. This was achieved by producing mixtures of EPDM graft polymers and polycarbonates dihydric phenols.

The invention relates to thermoplastic molding compositions the end

1. 5-95 wt .-% of graft polymers of styrene and / or their derivatives, styrene and / or derivatives in combination with acrylonitrile and / or their derivatives, methyl methacrylate and optionally styrene and / or acrylonitrile on EPDM rubbers.

2. 95-5% by weight of polycarbonates of dihydric phenols.

Le A 17 472

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• 2653U5

EPDM graft polymers T

EPDM graft polymers within the meaning of the invention are by Polymerization of the graft monomers obtained in the presence of the preformed EPDM rubber.

In principle, such products can be prepared using the known polymerization processes (Emulsion, solution, bulk, suspension, precipitation polymerization) as well as the resulting Combination processes can be synthesized.

EPDM rubbers, graft base

EPDM rubbers are copolymers of ethylene, Propylene and a non-conjugated diene understood. Included the ethylene: propylene weight ratio can be 75:25 to 40:60. The diene is in such quantities and such form in the Polymer incorporated that the methods used in rubber technology to determine the iodine number values from 2 to 30 deliver; this corresponds to a number of approx. 1-15 C bonds per 1000 carbon atoms. The copolymerization of the monomers can take place randomly or in segments.

Mixtures of several dienes can also be used instead of one diene.

Preferred dienes are: dicyclopentadiene, hexadiene (1,4) and 5-ethylidene norbornene-2. In principle, however, all diene components homologous to this are also suitable, such as alkylidene norbornene, Tricyclopentadiene, heptadiene, octadiene, etc.

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EPDM rubbers with a Mooney plasticity are particularly preferred (ML 1 + 4 ', 100 ° C) from 20-150, i.e. commercially available EPDM rubbers.

Graft monomers, graft polymers

For the purposes of this invention, graft monomers are styrene and mixtures of styrene and acrylonitrile and the derivatives both connections. Both monomers can be completely or partially replaced by methyl methacrylate. Of the derivatives of-methylstyrene and methacrylonitrile are particularly preferred.

When using styrene and acrylonitrile as graft monomers are monomer mixtures

styrene ₉

Acrylonitrile is preferred, and monomer ratios are particularly preferred

1 5 <

Acrylonitrile

The ratio of graft base to graft monomers can vary in the range

Graft base: Graft monomers = move 3:97 to 75:25.

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Graft reaction

The term "graft polymer" does not mean that the
graft monomers used are completely grafted onto the EPDM graft base. In the graft reactions which lead to the EPDM graft polymers according to the invention, more or less large amounts are formed
ungrafted homo- or copolymer. The amount of
Monomers actually grafted on and the molecular weight of the ungrafted polymer can be influenced within wide limits by a number of measures.

This primarily includes the selected polymerization process and, within the individual processes, the parameters:

Polymerization temperature, activator,

Molecular weight controller, time-controlled programs for temperature, Activator and monomer additive.

As in the graft reaction, only some of the monomers offered are really graft polymerized, it is also possible to use the EPDM graft polymers in a single or multi-stage process to produce, i.e. a graft polymer with a specified EPDM rubber content

- either by polymerizing the entire amount of graft monomer in the presence of the EPDM rubber in one stage
manufactured

- or by mixing a graft polymer with a higher EPDM content be obtained with a copolymer of the graft monomers.

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To achieve equivalent properties, depending on the procedure different polymerization conditions can be used.

The preferred polymerization method for manufacture of EPDM graft polymers is solution polymerization.

Instead of one graft polymer, it is also possible to use mixtures of different EPDM graft polymers are used that are within the given definition

a) regarding the relationship

Graft base graft monomers

and or

b) differ with regard to the EPDM graft bases used.

Instead of the pure EPDM graft polymers can also Mixtures of the graft polymers with polymers of the Graft monomers are used.

Isolation of the EPDM graft polymer

The isolation of the EPDM graft polymer depends on the manufacturing process for the graft polymer. It will the same process is used that is used for the isolation of the ABS polymers prepared analogously on an industrial scale be performed.

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The preferred solution polymerization process is isolation by stripping and removal of the solvent particularly suitable due to evaporation screws. In principle, the commercially available units of the Rubber and plastics technology are used.

Styrene-acrylonitrile copolymers ("SAN copolymers")

The styrene-acrylonitrile copolymers (if they are not formed during the graft polymerization) can after all Polymerization processes known for this purpose are produced.

The styrene can be completely or partially through, / - methylstyrene be replaced.

The SAN copolymer preferably contains styrene and acrylonitrile units in a weight ratio of 80:20 to 60:40. When styrene is replaced by A-methylstyrene, you have Copolymers with the weight ratio X -methylstyrene: Acrylonitrile = 69:31 has proven to be particularly favorable.

In the monomer combination of styrene and acrylonitrile, the styrene can also be completely or partially replaced by other monomers, or the acrylonitrile content can be increased to over 60% by weight in conjunction with other monomers. Examples of such modified SAN copolymers include terpolymers of styrene and acrylonitrile with methyl methacrylate, terpolymers of styrene and acrylonitrile with olefins d.

The styrene can also by ^ -Methylstyrene or by others Nuclear or side chain-substituted styrenes and the acrylonitrile can also be replaced by methacrylonitrile.

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The SAN copolymer can by various methods getting produced. If emulsion polymerization is used, the usual surface-active emulsifiers can be used Substances such as alkyl sulfates, alkyl sulfonates, aryl alkyl sulfonates, the alkali salts of saturated or unsaturated fatty acids and the alkali salts of disproportionated or hydrogenated abietin or Tall oil acids can be used. Possible activators are: Commercially available organic or inorganic peroxides, inorganic persulfates as well as redox systems, i.e. activator systems consisting of an oxidizing agent and Compose a reducing agent and heavy metal ions are additionally present in the reaction medium.

The molecular weights can be adjusted with so-called molecular weight regulators, mainly longer-chain mercaptans or terpinolene can be adjusted. Also by adding A regulation is possible for <* olefins.

In the case of polymerization in solution or as bulk polymerization, aromatic hydrocarbons can be used as solvents or the monomers themselves are used; suitable activators are organic peroxides or azo compounds.

If this process is only polymerized up to a certain conversion, the unconverted monomers can or the solvent e.g. via a screw evaporation or in the case of an emulsion polymerization can be removed from the solid polymer using a thin-film evaporator.

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If the styrene-acrylonitrile copolymers are produced by suspension polymerization, the commercially available dispersants such as
Polyvinyl alcohols, partially saponified polyvinyl acetate are used.

The polymerization process for the production of styrene-acrylonitrile copolymers or styrene polymers is not critical. For the preparation of the mixtures in the following examples Both commercial products and specially polymerized products were used.

The following parameters are used to characterize the products:

1. Acrylonitrile content; calculated using the N ₂ elemental analysis

2. styrene or o (-Me.thyJ.styrene content; calculated according to: 100 % -% acrylonitrile.

3. Mn = number average molecular weight, determined by

osmotic measurements,

4. Mw = weight average molecular weight, determined by

Light scattering,

5. U = J ^ - 1 (molecular non-uniformity)

6. MiJ ₁ = molecular weight from viscosity measurements (dimethyl

formamide, 20 ° C)

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Polycarbonates

Polycarbonates suitable according to the invention are: homopolycarbonates, (^ polycarbonates or mixtures of different homo- or copolycarbonates. The polycarbonates generally have Molecular weights from 10,000 to 200,000 (weight average M), preferably from 20,000 to 80,000 Two-phase interface processes abs phosgene and bisphenols or other processes are produced »as it is from the Literature (see H. Schnell, Chemistry and Physics of Polycarbonates, New York-London-Sydney, Interscience Publishers 1964, Polymer Reviews, Vol. 9 and U.S. Patents 3,028,365;

2 999 835; 3,148,172; 3,271,368; 2,991,273; 3,271,367;

3,780,078; 3 014 891 and 2 999 846).

The units in the aromatic polycarbonates according to the invention For example, the following bisphenols can be the basis:

Hydroquinone

Resorcinol

Dihydroxydiphenyls

Bis (hydroxyphenyl) alkanes

Bis (hydroxyphenyl) cycloalkane bis (hydroxyphenyl) sulfides

Bis (hydroxyphenyl) ether

Bis (hydroxyphenyl) ketones

Bis (hydroxyphenyl) sulfoxides bis (hydroxyphenyl) sulfones

"T, of · -Bis- (hydroxyphenyl) -diisopropylbenzenes.

Of these bisphenols, the following are preferred:

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2,2-bis- (4-hydroxyphenyl) -propane 2,4-bis- (4-hydroxyphenyl) -2-methylbutane 1,1-bis- (4-hydroxyphenyl) -cyclohexane <Γ, of '-Bis- ( 4-hydroxyphenyl) -p-diisopropybenzene 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane 2, 2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane 2, 2-bis (3-chloro-4-hydroxyphenyl) propane.

Particularly preferred polycarbonates are copolycarbonates based on 2,2-bis (4-hydroxyphenyl) propane and one of the others mentioned preferred bisphenols and polycarbonate based solely on 2,2-bis (4-hydroxyphenyl) propane.

These, as well as others for the production of aromatic Bisphenols suitable for polycarbonates are described in U.S. Patents 3,028,365; 2 999 835; 3,148,172; 3,271,368; 2,991,273; 3,271,367; 3,780,078; 3 014 891 and 2 999 846.

The polycarbonates can be produced by incorporating small amounts of polyhydroxy compounds, e.g. 0.05 - 2.0 mol% (based on the bisphenols used), be branched. Polycarbonates of this type are described, for example, in DT-OS 1 570 533; 2,116,973;

2,113,347; GB-PS 885 442; 1,079,821 and in U.S. Pat

3,544,514. Some of the polyhydroxy compounds that can be used are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) ) -heptane, 1,3,5-tri- (4-hydroxyphenyl) benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phe-, nylmethane, 2, 2-bis- / 4 '., 4- (4,4'-di-hydroxydiphenyl) -cyclohexylZ-pro pan, 2,4-bis- (4-hydroxyphenyl) -4-isopropyl ) -phenol , 2, 6- Bis- ( 2'-hydroxy-5'-methyl-benzyl) -4-methyl-phenol, 2,4-di-dihydroxybenzoic acid, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane and 1,4-bis (4 ·, 4 "-dihydroxy-triphenyl-methyl) -benzene.

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The molding compositions according to the invention can be prepared by intensive mixing of the components can be obtained. All known mixing methods can be used for this, such as mixing on rolling mills j in kneaders or in screw extruders.

The mixtures can also be carried out via the solution or slurry getting produced. For this purpose, the components are dissolved or slurried in suitable solvents or solvent mixtures and isolates the polymer mixtures with suitable nonsolvents. The solvents or solvent mixtures can can also be removed by evaporation.

The mixtures according to the invention can contain additives, in order to color and pigment the polymer mixtures, in order to ensure their resistance to oxidation, light resistance, and demoldability or to improve their flame resistance and the like. It can also be used in the mixes Fillers and reinforcing materials are incorporated.

In the following examples, parts and percentages are based on weight.

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Examples

The following base polymers were used as the starting point for the examples:

Production of EPDM graft polymers

The EPDM graft polymers are produced according to the following general recipe:

In L parts by weight of solvent

E parts by weight of EPDM rubber

solved. There are S parts by weight of styrene and

A parts by weight of acrylonitrile

added and the solution up

T ⁰ C (= polymerization temperature)

warmed up. After adding

I parts by weight of initiator is used for t hours

polymerized at the above-mentioned polymerization temperature T. The monomer sales achieved are * 98%. The polymer solution - based on the sum: E + S + A - 0.5 part by weight of a phenolic antioxidant (2,6-di-tert-butyl-p-cresol) and 0.5 part by weight of a costabilizer (dilauryl thiodipropionate) added and the polymer product by stripping isolated. The resulting crumbs are dried at 70 ° C. in a vacuum drying cabinet.

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Polymerization vessel: V2A steel, loadable up to 6 bar, more wall-compatible Stirrer designed for viscosities> 1000 poise.

Stripper:

commercial stripper of rubber technology.

The EPDM graft polymers are summarized in Table 1,

Since the monomer conversion is - 98%, it is for the further Discussion of the rubber content of the graft polymer equal to the amount of EPDM rubber (E) used in the Graft reaction set.

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Table 1

No. of EPDM

Graft polymer

III

IV

Solvent (L)

Art B. T T B. lot 500 300 300 500 EPDM rubber (E) Amount of rubber 45 45 45 29 If
Diene component DCPD DCPD EN DCPD Iodine number 12th 12th 24 12th Mooney value (ML 1 + 4 ¹ 100 ⁰ C) 70 70 90 70 Graft monomers Styrene (S) 41.3 41.3 41.3 53.2 Acrylonitrile (A) 13.7 13.7 13.7 17.8 Polymerization temperature (T) 120 115 120 120 Initiator (I) *** peroxide DTBP DTBP DTBP DTBP lot 0.9 0.9 0.9 0.9

Polymerization time

12th

14th

*) B = benzene, T = toluene,

* ♦) EN = 5-ethylidene-norbornene ~ 2-DCPD = dicyclopentadiene HX = hexadiene (1,4) '

***) DTBP

Di-tert-butyl peroxide

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The EPDM graft polymers given in the table below A to E were made from the EPDM graft polymers of Examples I to IV by mixing with a styrene-acrylonitrile copolymer manufactured.

The styrene-acrylonitrile copolymer is characterized by the following data:

Acrylonitrile content: 26.2% Styrene content: 73.8% M _M : 120,000

Mw Mn

2.1

The mixtures are produced at 160 ° C. on the roller.

The EPDM graft polymer F was produced according to Example XII / 2 of DOS 1,769,052;
Rubber content: 11.5%.

The EPDM graft polymer G was produced according to Example 1 of DOS 2 302 014;
Rubber content: 10.4%.

EPDM graft polymer

Parts of EPDM graft polymer from example
(I to IV)

Parts of styrene acrylonitrile copolymer

A. 60 (IV) B. 40 (I) C. 30 (II) D. 20 (III) E. 10 (II) Le A 17 472 - 15 - 80982 1/0468

40 60 70 80 90

2653U5 42

Examples 1 to 16

The polycarbonates used were two polymers PC 2800 and PC 3200, made from 2,2-bis- (4-hydroxyphenyl) propane with different Molecular weight used. The relative viscosity of PC 2800 was 1.28 and that of PC 3200 was 1.32. Measured was the relative viscosity of a solution of 0.5 g of polycarbonate in 100 ml of methylene chloride at 23 ° C.

The production of the blends with the EPDM graft polymers A to G took place in a single-screw extruder at temperatures of 200, 240, 245 and 240 ° C. the Mixing ratios are given in the following tables.

The polymer blends thus obtained were at one melt temperature sprayed from 25O ° C to test specimens. Some mechanical and thermal properties of the mixtures will be summarized in the following two tables.

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example 1 2 3 4th 5 6th 7th 8th Mix 60 A 60 B 60 C 60 D 50 B 50 C 50 D 50 E relationship 40 pc 2800 40 rc 2800 40 rc 2800 40 rc 2800 50 rc 2800 50 rc 2800 50 rc 2800 50 rc 2800 a RP
η _ ung. ung. ung. ung. ung. ung. ung. ung. -4O ° C ung. ung. ung. ung. ung. ung. ung. ung. a RT 51 ung. 6/43 14th 3/65 3/47 27 11 -40 ° C 4th 5 4th 3 6th 5 3 3 B-E-M 2140 1960 2180 2370 1900 2030 2170 2320 80 78 87 95 79 86 93 102 f 4.6 4.8 4.7 4.7 5.0 4.8 4.8 4.9 Vicat 105 107 108 108 110 111 112 114 HC 30 84 96 116 137 99 116 131 146

ςτ> ■ pi

O CD CD

example Vicat 9 10 11 12th 13th 14th 15th 16 Mix
relationship HC 30 40 p
60 pc 2800 40 G
60 pc 2800 60 B
40 pc 3200 60 C
40 pc 3200 60 D
40 pc 3200 50 B
50 pc 3200 50 C
50 pc 3200 50 D
50 pc 3200 a RT
η Ung. ung. ung. ung. ung. ung. ung. ung. -40 ° C ung. ung. ung. ung. ung. ung. ung. ung. a RT 64 18th 49 40 24 59 36 29 -40 ° C 5 3 4th 4th 3 3 3 3 B-E-M 2360 2240 2120 23OO 2480 1970 2130 2290 100 94 78 86 95 81 88 95 f 5.1 5.1 5.9 5.9 5.9 5.0 4.9 4.8 123 119 107 108 109 111 112 113 115 114 83 99 112 86 100 112

In the table:

- 2
a: impact strength according to DIN 53 453; Dimension / kJ / m /

~~~ ung .: unbroken; RT: room temperature; 6/43: 6 out of 10 standard rods break in one

2 average impact stress of 43 kJ / m,

the rest doesn't break.

a _k s Notched impact strength according to DIN 53 453? Dimensions / kJ / m_ /.

BE-MsB iege elasticity modulus measured "with three-point load? Dimensions / N / mm 7»

G " _faF s bending flow stress according to DIN 53 452? Dimension: / N / mm J,

-t_A deflection atG,; Dimension; / ran /.

¥ icat % Vicat softening temperature according to method B (force 49.05 H) according to DIN 53 460? Dimensions / ⁰ C /.

HC 30 s ball indentation hardness after 30 seconds, according to DIW 53 456? - Dimensions / SJ / mm / _o

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Claims (8)

2653U5 claims First Thermoplastic molding compounds (A) 5-9 5 wt .-% of graft polymers of styrene and / or its derivatives, styrene and / or its derivatives in combination with acrylonitrile and / or its derivatives, Methyl methacrylate and optionally styrene and / or acrylonitrile on EPDM rubbers and (B) 95-5 wt% of dihydric phenol polycarbonates. 2. Molding compositions according to claim 1, characterized in that the graft polymers are in an aromatic solvent or have been prepared in an aromatic solvent mixture. 3. Molding compositions according to claim 2, characterized in that in the preparation of the graft polymer A) the following Conditions are met: ₁ , solvent {10 Sum of the reactants 0 33 < graft base 'graft monomers _{1 <} Styrene Acrylonitrile Polymerization temperature> 8O ⁰ C. Le A 17 472 - 20 - 809821 / CHB8 ORIGINAL 2653 I Fig 4. Molding compositions according to claim 3, characterized in that the diene component in LPDM rubber is 5-ethylidene-norbornene-2 _/ dicyclopeatdiene or hexadiene- (1,4). 5. Molding compounds gi measure claim 1 --1, characterized in that that the t'oLycaLboiiaten a:> the several bisphenols from the Use the following as a basis: 2,2-bis (4-hydroxyphenyl) propane
2,4-bis- (4-hydroxyphenyl) -2-methy! Butane 1,1-bis- (4-hydroxyphenyl) -cyclohexane o ^ oC'-bis-CA-hydroxypheriyO-p-diisopropylbenzene 2,2-bis- (}, 5-dichloro-! -Hydroxyphenyl) -propane 2, 2-bis- (3, ^c 3-dibromo-4-hydroxyphenyl) -propane 2,2-bis- (J-chloro-4-hydroxyphenyl) -propane . 6. Molding compositions according to claims 1-5, characterized in that the polycarbonates are 2,2-bis (4-hydroxyphenyl) propane and one of the other bisphenols mentioned in claim 5 are based. 7. Molding compositions according to claims 1-5, characterized in that the polycarbonates alone 2,2-bis- (4-hydroxyphenyl) -propane or 2,4-bis- (4-hydroxyphenyl) -2-methylbutane or λ, Χ ¹ -bis- (4-hydroxyphenyl) -p-diisopropylbenzene are based. 8. Molding compositions according to claims 1-4, characterized that the graft polymer A) contains styrene and acrylonitrile grafted onto an EPDM rubber. Le A 17 472 - 2 1 - Π 9 B? I / Π L RR ORIGINAL INSPECTED